Mask blank, phase-shift mask, and method of manufacturing semiconductor device

ABSTRACT

A mask blank is provided in which a phase-shift film is provided on a transparent substrate, the phase-shift film having a predetermined transmittance to ArF exposure light and being configured to shift a phase of ArF exposure light transmitted therethrough, wherein the phase-shift film comprises a nitrogen-containing layer that is formed from a material containing silicon and nitrogen and does not contain a transition metal, and wherein a content of oxygen in the nitrogen-containing layer, when measured by X-ray photoemission spectroscopy, is below a detection limit.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a Continuation of application Ser. No. 16/201,344, filed on Nov.27, 2018, which is a Continuation of application Ser. No. 15/454,199,filed Mar. 9, 2017, which is a Continuation of application Ser. No.14/760,911, filed Jul. 14, 2015, claiming priority based onInternational Application No. PCT/JP2014/050404, filed Jan. 14, 2014,the contents of all of which are incorporated herein by reference intheir entirety. International Application No. PCT/JP2014/050404 claimspriority based on Japanese Patent Application Nos. 2013-004370, filedJan. 15, 2013, 2013-046721, filed Mar. 8, 2013, and 2013-112549, filedMay 29, 2013.

TECHNICAL FIELD

The present disclosure relates to a mask blank, a phase-shift maskmanufactured using that mask blank, and methods for manufacturing thesame.

BACKGROUND ART

In general, the formation of a fine pattern in the manufacturing processof semiconductor devices is carried out using photolithography. Inaddition, multiple substrates referred to as transfer masks are normallyused to form this fine pattern. In miniaturizing the pattern of asemiconductor device, it is necessary to use a short wavelength for thewavelength of the exposure light source used in photolithography inaddition to miniaturizing the mask pattern formed on the transfer mask.In recent years, increasingly shorter wavelengths are being used asindicated by the transition from KrF excimer lasers (wavelength: 248 nm)to ArF excimer lasers (wavelength: 193 nm) for use as the exposure lightsource during the manufacturing of semiconductor devices.

Known types of transfer masks include conventional binary masks,provided with a light shielding pattern composed of a chromium-basedmaterial on a transparent substrate, and halftone phase-shift masks.Molybdenum silicide (MoSi)-based materials are widely used for thephase-shift film of halftone phase-shift masks. However, as disclosed inPatent Literature 1, MoSi-based films have recently been determined toexhibit low fastness to exposure light of an ArF excimer laser(so-called ArF light fastness). In Patent Literature 1, ArF lightfastness is enhanced by carrying out plasma treatment, UV radiationtreatment or heat treatment on an MoSi-based film following patternformation, for forming a passive film on the surface of the MoSi-basedfilm pattern.

Patent Literature 2 discloses a photo mask blank having a transitionmetal-silicon-based material film composed of a material containing atransition metal, silicon, oxygen and nitrogen. In this PatentLiterature 2 as well, when exposure light of an ArF excimer laser (ArFexposure light) is radiated for a long period of time onto a transitionmetal-silicon-based material film having a pattern formed thereon, thetechnical problem arises in which a phenomenon occurs that causes achange in the pattern line width. On the other hand, Patent Literature 3discloses a phase-shift mask provided with a phase-shift film composedof SiNx.

PRIOR ART LITERATURE Patent Literature

Patent Literature 1: JP 2010-217514A

Patent Literature 2: JP 2012-58593A

Patent Literature 3: JP H8-220731A

DISCLOSURE OF THE DISCLOSURE Problems to be Solved by the Disclosure

The method used to improve ArF light fastness in which a passive film isformed on the surface of a pattern formed with an MoSi-based film inPatent Literature 1 does not change the internal structure of theMoSi-based film. In other words, ArF light fastness can be said to beequivalent to that of the prior art with respect to the interior of theMoSi-based film. Consequently, it is necessary to form a passive filmnot only on the surface layer of the upper surface of the MoSi-basedfilm pattern, but also on the surface layers of the sidewalls. In PatentLiterature 1, after having formed a pattern on the MoSi-based film, apassive film is formed by carrying out plasma treatment, UV radiationtreatment or heat treatment. However, the pattern formed on theMoSi-based film has a large difference in in-plane coarseness andfineness and distances between side walls of adjacent patternsfrequently differ greatly. Consequently, there was the problem that itis not easy to form passive films of the same thickness on the sidewallsof all patterns.

In the transition metal-silicon-based material film in Patent Literature2, ArF light fastness is indicated as being able to be improved as aresult of making the oxygen content in the film to be not less than 3 at%, making the content of silicon and the content of transition metal tobe within a range that satisfies a predetermined relational expression,and employing a configuration in which an oxidized surface layer isprovided on the surface layer of this transition metal-silicon-basedmaterial film. ArF light fastness can therefore be expected to beimproved beyond that of conventional transition metal-silicon-basedmaterial films. There is a promising hypothesis that the change(increase) in line width in a pattern composed of a transitionmetal-silicon-based material film accompanying irradiation with an ArFexcimer laser is caused by instability of the transition metal in thefilm during photoexcitation as a result of being irradiated by an ArFexcimer laser. Consequently, the transition metal-silicon-based materialfilm of Patent Literature 2 also had the problem that it is difficult toadequately resolve the problem of ArF light fastness as long as the filmcontains a transition metal.

In addition, it is essential that the transition metal-silicon-basedmaterial film in this Patent Literature 2 contains oxygen. The degree ofthe increase in transmittance with respect to ArF exposure lightaccompanying the containing of oxygen in the film is quite large incomparison with nitrogen. Consequently, there is the problem of beingunable to avoid an increase in film thickness in comparison with atransition metal-silicon-based material film that does not containoxygen (such as an MoSiN-based film).

On the other hand, in the case of a film composed of SiNx not containinga transition metal as described in Patent Literature 3, when that havinga pattern formed on this SiNx film was attempted to be irradiated withan ArF excimer laser for a long period of time, the change (increase) inpattern width was extremely small in comparison with a transitionmetal-silicon-based material film, and this film was able to beconfirmed to have high ArF light fastness through verification by theinventor of the present disclosure. However, it is not easy to applythis SiNx film to a halftone phase-shift film suitable for ArF exposurelight.

Halftone phase-shift films (to also be simply referred to as“phase-shift films”) are required to have a function to transmit ArFexposure light therethrough at a predetermined transmittance andgenerate a predetermined phase difference between the ArF exposure lightthat transmits through the phase-shift film and light that transmitsthrough air over the same distance as the thickness of the phase-shiftfilm. In the case of forming a single layer of a phase-shift film, it isrequired to use a material for which the refractive index n with respectto ArF excimer laser light is somewhat large and the extinctioncoefficient k is somewhat small. Although silicon is a material having asomewhat large extinction coefficient k with respect to ArF excimerlaser light, refractive index n of silicon has a tendency to be quitesmall. Transition metals are materials that have a tendency for both theextinction coefficient k and the refractive index n to be large withrespect to ArF exposure light. In addition, in the case oxygen iscontained in a film material, the extinction coefficient k with respectto ArF exposure light decreases considerably and the refractive index nalso demonstrates a decreasing trend. In the case of containing nitrogenin a film material, although the extinction coefficient k with respectto ArF exposure light decreases, the refractive index n demonstrates anincreasing trend.

As a result of having the optical characteristics of each element asdescribed above, in the case of forming a phase-shift film with aconventional transition metal-silicon-based material, since thephase-shift film contains a transition metal that is a material forwhich both refractive index n and extinction coefficient k are large,even if oxygen is contained to a certain degree or the content ofnitrogen is reduced to a certain degree, a predetermined transmittanceand phase difference can be secured. In contrast, in the case of forminga phase-shift film with a silicon-based material that does not contain atransition metal, since silicon is a material for which refractive indexn is quite small, a larger amount of nitrogen, which is an element thatincreases refractive index, must be contained in comparison with aconventional transition metal-silicon-based material. In addition, sinceincreasing the content of nitrogen causes the transmittance of thephase-shift film to change in an increasing direction, it is necessaryto reduce the content of oxygen in the phase-shift film to an extremelylow level. In this manner, there are more restrictions placed on theformation of a phase-shift film having a single layer structure with asilicon-based material in the manner of SiNx that does not contain atransition metal in comparison with the prior art.

In general, not only phase-shift films, but also thin films for forminga pattern on a mask blank, are formed using a sputtering method. In thecase of forming a thin film on a transparent substrate by a sputteringmethod, conditions are normally selected that allow a film to bedeposited comparatively stably. For example, in the case of depositingan SiNx film by sputtering, deposition is carried out by a process inwhich an Si target is arranged in a film deposition chamber, and Siparticles, which have been scattered as a result of continuouslycirculating a mixed gas of nitrogen and a noble gas such as Ar whilecolliding the plasmified noble gas with the Si target, incorporatenitrogen at an intermediate point in the process and are deposited on atransparent substrate (this type of sputtering is typically referred toas “reactive sputtering”). The nitrogen content of the SiNx film can beadjusted mainly by increasing or decreasing the mixing ratio of nitrogenin the mixed gas, and as a result thereof, SiNx films having variousnitrogen contents can be deposited on a transparent substrate.

However, there are cases in which stable deposition is possible andcases in which stable deposition is difficult depending on the mixingratio of nitrogen in the mixed gas. For example, in the case ofdepositing an SiNx film by reactive sputtering, the SiNx film can bedeposited comparatively stably in the case the nitrogen gas mixing ratioin the mixed gas is such that a stoichiometrically stable Si₃N₄ film, orfilm having a nitrogen content close thereto, is formed (a region havingsuch deposition conditions is referred to as the “poison mode” or“reaction mode”, see FIG. 4). In addition, the SiNx film can also bedeposited comparatively stably in the case the nitrogen gas mixing ratioin the mixed gas is such that a film is formed that has a low nitrogencontent (and a region having such deposition conditions is referred toas the “metal mode”, see FIG. 4). On the other hand, deposition easilybecomes unstable and uniformity of the composition and opticalcharacteristics of the SiNx film in the in-plane direction and directionof film thickness decreases, or defects in the formed film occurfrequently, in the case the nitrogen gas mixing ratio in the mixed gasis intermediate to this poison mode and metal mode (and a region havingsuch deposition conditions is referred to as the “transition mode”, seeFIG. 4). In addition, uniformity of the composition and opticalcharacteristics of the SiNx film between substrates also tends todecrease in the case of respectively depositing SiNx films on aplurality of transparent substrates. In the case of forming aphase-shift film to which ArF exposure light is applied with a singlelayer structure of SiNx, there was the problem that it is frequentlynecessary to deposit the film by reactive sputtering in a region of thetransition mode where deposition easily becomes unstable.

Therefore, in order to solve the problems of the prior art, an aspect ofthe present disclosure is to provide a mask blank provided with aphase-shift film on a transparent substrate, wherein, even in the caseof applying a silicon-based material that does not contain a transitionmetal, which causes a decrease in ArF light fastness, for the materialused to form the phase-shift film, uniformity of the composition andoptical properties of that phase-shift film in the in-plane directionand direction of film thickness is high, uniformity of the compositionand optical characteristics of the phase-shift film between a pluralityof substrates is also high, and defectivity is low. In addition, anaspect of the present disclosure is to provide a phase-shift maskmanufactured using this mask blank. Moreover, an aspect of the presentdisclosure is to provide a method for manufacturing the mask blank and amethod for manufacturing the phase-shift mask.

Means for Solving the Problems

The present disclosure has the configurations indicated below in orderto achieve the aforementioned aspects.

Configuration 1 of the present disclosure is a mask blank in which aphase-shift film is provided on a transparent substrate, the phase-shiftfilm having a function to transmit ArF exposure light therethrough at apredetermined transmittance and a function to generate a predeterminedamount of phase shift in the ArF exposure light that is transmittedtherethrough; wherein,

the phase-shift film comprises a structure in which a low transmissionlayer and a high transmission layer are laminated,

the low transmission layer and the high transmission layer are formedfrom a material consisting of silicon and nitrogen or a materialconsisting of silicon, nitrogen and one or more elements selected fromsemi-metallic elements, non-metallic elements and noble gases, and

the low transmission layer has a relatively low nitrogen content incomparison with the high transmission layer.

Configuration 2 of the present disclosure is as follows. Namely,Configuration 2 is the mask blank described in Configuration 1, whereinthe low transmission layer and the high transmission layer are composedof the same constituent elements.

Configuration 3 of the present disclosure is as follows. Namely,Configuration 3 is the mask blank described in Configuration 1 orConfiguration 2, wherein the phase-shift film has two or more sets of alaminated structure composed of one layer of the low transmission layerand one layer of the high transmission layer.

Configuration 4 of the present disclosure is as follows. Namely,Configuration 4 is the mask blank described in any of Configurations 1to 3, wherein the low transmission layer and the high transmission layerare formed from a material consisting of silicon and nitrogen.

Configuration 5 of the present disclosure is as follows. Namely,Configuration 5 is the mask blank described in any of Configurations 1to 4, wherein the low transmission layer is formed from a materialhaving a refractive index n with respect to ArF exposure light of lessthan 2.5 and an extinction coefficient k with respect to ArF exposurelight of not less than 1.0, and the high transmission layer is formedfrom a material having a refractive index n with respect to ArF exposurelight of not less than 2.5 and an extinction coefficient k with respectto ArF exposure light of less than 1.0.

Configuration 6 of the present disclosure is as follows. Namely,Configuration 6 is the mask blank described in any of Configurations 1to 5, wherein the thickness of a single layer of each of the lowtransmission layer and the high transmission layer is not more than 20nm

Configuration 7 of the present disclosure is as follows. Namely,Configuration 7 is the mask blank described in any of Configurations 1to 6, wherein the phase-shift film is provided with an uppermost layerformed at a position farthest away from the transparent substrate, andthe uppermost layer is formed from a material consisting of silicon,nitrogen and oxygen, or a material consisting of silicon, nitrogen,oxygen and one or more elements selected from semi-metallic elements,non-metallic elements and noble gases.

Configuration 8 of the present disclosure is as follows. Namely,Configuration 8 is the mask blank described in Configuration 7, whereinthe uppermost layer is formed from a material consisting of silicon,nitrogen and oxygen.

Configuration 9 of the present disclosure is a phase-shift mask in whicha transfer pattern is formed on the phase-shift film of the mask blankdescribed in any of Configurations 1 to 8.

Configuration 10 is a method for manufacturing a mask blank providedwith a phase-shift film on a transparent substrate, the phase-shift filmhaving a function to transmit ArF exposure light therethrough at apredetermined transmittance and a function to generate a predeterminedamount of phase shift in the ArF exposure light that is transmittedtherethrough;

wherein the phase-shift film comprises a structure in which a lowtransmission layer and a high transmission layer are laminated,

wherein the method comprises:

a low transmission layer formation step of forming the low transmissionlayer on or above the transparent substrate by reactive sputtering in asputtering gas comprising a nitrogen-based gas and a noble gas using asilicon target or a target composed of a material consisting of siliconand one or more elements selected from semi-metallic elements andnon-metallic elements, and

a high transmission layer formation step of forming the hightransmission layer on or above the transparent substrate by reactivesputtering in a sputtering gas comprising a nitrogen-based gas and anoble gas, and the sputtering gas having a higher mixing ratio ofnitrogen-based gas than the mixing ratio of nitrogen-based gas in thesputtering gas for the low transmission layer formation step, using asilicon target or a target composed of a material consisting of siliconand one or more elements selected from semi-metallic elements andnon-metallic elements.

Configuration 11 of the present disclosure is as follows. Namely,Configuration 11 is the method for manufacturing a mask blank describedin Configuration 10, wherein a mixing ratio of nitrogen-based gasselected for the sputtering gas used in the low transmission layerformation step is lower than the range of nitrogen-based gas mixingratios at which deposition is in a transition mode in which depositionhas a tendency to become unstable, and

a mixing ratio of nitrogen-based gas selected for the sputtering gasused in the high transmission layer formation step is higher than therange of nitrogen-based gas mixing ratios at which deposition is in thetransition mode.

Configuration 12 of the present disclosure is as follows. Namely,Configuration 12 is the method for manufacturing a mask blank describedin Configuration 10 or Configuration 11, wherein the low transmissionlayer formation step forms the low transmission layer by reactivesputtering in a sputtering gas consisting of nitrogen gas and a noblegas using a silicon target, and the high transmission layer formationstep forms the high transmission layer by reactive sputtering in asputtering gas consisting of nitrogen and a noble gas using a silicontarget.

Configuration 13 of the present disclosure is as follows. Namely,Configuration 13 is the method for manufacturing a mask blank describedin any of Configurations 10 to 12, wherein the low transmission layer isformed from a material having a refractive index n with respect to ArFexposure light of less than 2.5 and an extinction coefficient k withrespect to ArF exposure light of not less than 1.0, and the hightransmission layer is formed from a material having a refractive index nwith respect to ArF exposure light of not less than 2.5 and theextinction coefficient k with respect to ArF exposure light of less than1.0.

Configuration 14 of the present disclosure is the method formanufacturing a mask blank described in any of Configurations 10 to 13,further comprising an uppermost layer formation step of forming anuppermost layer, at a position of the phase-shift film farthest awayfrom the transparent substrate, by reactive sputtering in a sputteringgas comprising a noble gas using a silicon target or a target composedof a material consisting of silicon and one or more elements selectedfrom semi-metallic elements and non-metallic elements.

Configuration 15 of the present disclosure is the method formanufacturing a mask blank described in Configuration 12, furthercomprises an uppermost layer formation step of forming an uppermostlayer, at a position of the phase-shift film farthest away from thetransparent substrate, by reactive sputtering in a sputtering gascomposed of nitrogen gas and a noble gas using a silicon target, andcarrying out treatment in which at least the surface layer of theuppermost layer is oxidized.

Configuration 16 of the present disclosure is a method for manufacturinga phase-shift mask, comprising: a step of forming a transfer pattern inthe phase-shift film of a mask blank manufactured according to themethod for manufacturing a mask blank described in any of Configurations10 to 15.

Effects of the Disclosure

The mask blank of the present disclosure is a mask blank provided with aphase-shift film on a transparent substrate, the phase-shift film havinga function to transmit ArF exposure light therethrough at apredetermined transmittance and generate a predetermined amount of aphase shift in the ArF exposure light that is transmitted therethrough,wherein the phase-shift film comprises a structure in which a lowtransmission layer and a high transmission layer are laminated, the lowtransmission layer and the high transmission layer are formed from amaterial composed of silicon and nitrogen or a material consisting ofsilicon, nitrogen and one or more elements selected from semi-metallicelements, non-metallic elements and noble gases, and the lowtransmission layer has a relatively low nitrogen content in comparisonwith the high transmission layer. As a result of employing a mask blankhaving such a structure, a low transmission layer composed of a materialhaving a low nitrogen content can be deposited by reactive sputteringunder deposition conditions enabling stable deposition using a mixed gashaving a low nitrogen gas mixing ratio for the sputtering gas, while ahigh transmission layer composed of a material having a high nitrogencontent can be deposited by reactive sputtering under depositionconditions enabling stable deposition using a mixed gas having a highnitrogen gas mixing ratio for the sputtering gas. As a result, a masksubstrate can be realized in which uniformity of the composition andoptical characteristics of the phase-shift film in the in-planedirection and direction of film thickness can be made to be high,uniformity of the composition and optical characteristics of thephase-shift film between a plurality of substrates can also be made tobe high, and defectivity can be made to be low.

In addition, the method for manufacturing a mask blank of the presentdisclosure is a method for manufacturing a mask blank provided with aphase-shift film on a transparent substrate, the phase-shift film havinga function to transmit ArF exposure light therethrough at apredetermined transmittance and generate a predetermined amount of phaseshift in the ArF exposure light that is transmitted therethrough,wherein the phase-shift film comprises a structure in which a lowtransmission layer and a high transmission layer are laminated, and themethod comprises: a low transmission layer formation step of forming thelow transmission layer on or above the transparent substrate by reactivesputtering in a sputtering gas comprising a nitrogen-based gas and anoble gas using a silicon target or a target composed of a materialconsisting one or more elements selected from semi-metallic elements andnon-metallic elements in silicon, and a high transmission layerformation step of forming the high transmission layer on or above thetransparent substrate by reactive sputtering in a sputtering gascomprising a nitrogen-based gas and a noble gas, and the sputtering gashaving a higher mixing ratio of nitrogen-based gas than the mixing ratioof nitrogen-based gas in the sputtering gas for the low transmissionlayer formation step, using a silicon target or a target composed of amaterial consisting one or more elements selected from semi-metallicelements and non-metallic elements in silicon. As a result of employingthis method for manufacturing a mask blank, a low transmission layercomposed of a material having a low nitrogen content can be deposited byreactive sputtering under deposition conditions enabling stabledeposition using a mixed gas having a low nitrogen-based gas mixingratio for the sputtering gas, while a high transmission layer composedof a material having a high nitrogen content can be deposited byreactive sputtering under deposition conditions enabling stabledeposition using a mixed gas having a high nitrogen-based gas mixingratio for the sputtering gas. As a result, a mask blank can bemanufactured in which uniformity of the composition and opticalcharacteristics of the phase-shift film in the in-plane direction anddirection of film thickness can be made to be high, uniformity of thecomposition and optical characteristics of the phase-shift film betweena plurality of substrates can be made to be high, and defectivity can bemade to be low.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view showing the configuration of a maskblank in a first and second embodiment.

FIG. 2 is a cross-sectional view showing another configuration of a maskblank in a first and second embodiment.

FIGS. 3A-3F are cross-sectional views showing a process formanufacturing a transfer mask in a first embodiment and secondembodiment.

FIG. 4 is a schematic diagram for explaining deposition modes in thecase of forming a thin film by reactive sputtering.

FIG. 5 is a flow chart showing a method for manufacturing a mask blankin a second embodiment.

FIG. 6 is a schematic diagram showing one example of an RF sputteringapparatus used in a manufacturing method in a second embodiment.

FIG. 7 is a cross-sectional view showing the configuration of a maskblank in a third embodiment.

FIG. 8 is a schematic diagram showing one example of a depositionapparatus used in a method for manufacturing a mask blank in a thirdembodiment.

FIG. 9 is a schematic diagram showing the positional relationshipbetween a substrate and a sputtering target in a deposition apparatusused in a method for manufacturing a mask blank in a third embodiment.

FIG. 10 is a cross-sectional view showing the configuration of aphase-shift mask in a third embodiment.

EMBODIMENTS FOR CARRYING OUT THE DISCLOSURE First Embodiment

The following provides an explanation of a first embodiment of thepresent disclosure.

The inventors of the present disclosure conducted extensive studies on ameans for realizing a film that exhibits high uniformity of compositionand optical characteristics in the direction of film thickness and haslow defectivity in the case of forming a phase-shift film with asilicon-based material film that contains silicon and nitrogen but doesnot contain a transition metal. At the present level of film depositiontechnology, it is necessary to apply a film deposition technology thatemploys reactive sputtering in order to form a silicon-based materialfilm containing silicon and nitrogen but not containing a transitionmetal on a substrate in a state in which uniformity of composition andoptical characteristics is high. However, typically in the case ofdepositing a thin film by reactive sputtering, a phenomenon occasionallyoccurs in which the thin film deposition rate and voltage fluctuateaccording to the mixing ratio of the reactive gas in the film depositionchamber.

FIG. 4 is a graph schematically indicating typical trends with respectto changes in deposition rate that occur when the mixing ratio of areactive gas in a mixed gas (or flow rate ratio of a reactive gas in amixed gas) composed of a noble gas and a reactive gas in a depositionchamber has been changed in the case of depositing a thin film byreactive sputtering. FIG. 4 depicts a curve I of the change in filmdeposition rate in the case the mixing ratio of the reactive gas in themixed gas has been increased gradually (increase mode), and a curve D ofthe change in film deposition rate in the case the mixing ratio of thereactive gas in the mixed gas has been decreased gradually (decreasemode). In general, in a region in which the mixing ratio of the reactivegas in the mixed gas is low (region of metal mode M in FIG. 4) and aregion in which the mixing ratio of the reactive gas in the mixed gas ishigh (region of reaction mode R in FIG. 4), the size of the fluctuationin film deposition rate accompanying a change in the reactive gas mixingratio in the mixed gas is small in both the increase mode and decreasemode. In addition, the difference in film deposition rate between theincrease mode and decrease mode for the mixing ratio of the reactive gasin the same mixed gas is also small. Consequently, a thin film can bedeposited stably in the region of the metal mode M and the region of thereaction mode R. Namely, the region of the metal mode M and the regionof the reaction mode R can be said to be regions that allow theformation of a thin film that has high uniformity of composition andoptical characteristics and has low defectivity.

On the other hand, in the region of a transition mode T interposedbetween the region of the metal mode M and the region of the reactionmode R, the size of the fluctuation in deposition rate accompanying achange in the reactive gas mixing ratio in the mixed gas is large inboth the increase mode and decrease mode. In addition, the difference indeposition rate between the increase mode and decrease mode is alsolarge for the reactive gas mixing ratio in the same mixed gas. In theregion of the transition mode T, fluctuations in deposition rateattributable to a slight change in reactive gas mixing ratio in themixed gas in the deposition chamber are large, and fluctuations indeposition rate caused by a shift from the increase mode to the decreasemode also occur due to slight changes in the mixing ratio. Consequently,thin films are formed in a state in which deposition rate is unstable.Fluctuations in deposition rate have an effect on the amounts ofcomponents of the reactive gas contained in the thin film. Namely, theregion of the transition model T can be said to be a region in which itis difficult to form a thin film having high uniformity of compositionand optical characteristics and low defectivity.

In the case of forming a phase-shift film having a single layerstructure composed of a silicon-based material film not containing atransition metal by reactive sputtering, it is highly necessary todeposit the film in the region of the transition mode T due torestrictions on the required optical characteristics. There are alsomethods used to search for a combination of reactive gases for which thedifference in deposition rate between the increase mode and decreasemode is small in the transition mode T for a reactive gas mixing ratioin the same mixed gas. However, even if such a combination of reactivegases was to be found, the problem of large fluctuations in depositionrate accompanying changes in the reactive gas mixing ratio in the mixedgas in the transition mode T is not solved.

In the case of forming a silicon-based material film containing siliconand nitrogen but not containing a transition metal by reactivesputtering in the region of the metal mode M, when film thickness isattempted to be secured for obtaining a required phase difference as aphase-shift film, since the extinction coefficient k of this filmmaterial formed is high, transmittance with respect to ArF exposurelight ends up being lower than the required transmittance. In the caseof such a film, it is difficult to generate phase-shift effects and thefilm is not suitable for a phase-shift film. On the other hand, in thecase of forming a silicon-based material film containing silicon but notcontaining a transition metal by reactive sputtering in the region ofthe reaction mode, when film thickness is attempted to be secured toobtain a required phase difference as a phase-shift film, since theextinction coefficient k of the film material formed is low,transmittance with respect to ArF exposure light ends up being higherthan the required transmittance. Although this type of film allows theobtaining of phase-shift effects, there is the risk of the resist filmon the semiconductor wafer being sensitized by light transmitted from aportion of the pattern other than the region where phase-shift effectsare generated, and this also makes this film unsuitable for aphase-shift film.

As a result of conducting extensive studies on a means for solving thenumerous technical problems that occur in the realizing of a phase-shiftfilm that is suitable for ArF exposure light with a silicon-basedmaterial film containing silicon and nitrogen but not containing atransition metal, the conclusion was reached that the aforementionedtechnical problems can be solved by using a phase-shift film having astructure obtained by laminating a low transmission layer, which is asilicon-based material film formed by reactive sputtering according tothe region of the metal mode, and a high transmission layer, which is asilicon-based material film formed by reactive sputtering according tothe region of the reaction mode.

Namely, the present disclosure is a mask blank provided with aphase-shift film on a transparent substrate, the phase-shift film havinga function to transmit ArF exposure light therethrough at apredetermined transmittance and generate a predetermined amount of phaseshift in the ArF exposure light that is transmitted therethrough. Themask blank of the present disclosure comprises the followingcharacteristics. Namely, the phase-shift film comprises a structure inwhich a low transmission layer and a high transmission layer arelaminated. In addition, the low transmission layer and the hightransmission layer are formed from a material consisting of silicon andnitrogen or a material consisting of silicon, nitrogen and one or moreelements selected from semi-metallic elements, non-metallic elements andnoble gas. In addition, the low transmission layer has a relatively lownitrogen content in comparison with the high transmission layer.

In addition, the present disclosure is a method for manufacturing a maskblank provided with a phase-shift film on a transparent substrate, thephase-shift film having a function to transmit ArF exposure lighttherethrough at a predetermined transmittance and generate apredetermined amount of phase shift in the ArF exposure light that istransmitted therethrough. The aforementioned phase-shift film comprisesa structure in which a low transmission layer and high transmissionlayer are laminated. The method for manufacturing a mask blank of thepresent disclosure comprises a low transmission layer formation step anda high transmission layer formation step. In the low transmission layerformation step, the low transmission layer is formed on or above thetransparent substrate by reactive sputtering in a sputtering gascomprising a nitrogen-based gas and a noble gas using a silicon targetor a target composed of a material consisting one or more elementsselected from semi-metallic elements and non-metallic elements insilicon. In the high transmission layer formation step, the hightransmission layer is formed on or above the transparent substrate byreactive sputtering in a sputtering gas comprising a nitrogen-based gasand a noble gas, and the sputtering gas having a higher mixing ratio ofnitrogen-based gas than the mixing ratio of nitrogen-based gas in thesputtering gas for the low transmission layer formation step, using asilicon target or a target composed of a material consisting of one ormore elements selected from semi-metallic elements and non-metallicelements in silicon.

In addition, in this method for manufacturing a mask blank, anitrogen-based gas mixing ratio is preferably selected for thesputtering gas used in the low transmission layer formation step whichis lower than the range of nitrogen-based gas mixing ratios at whichdeposition is in a transition mode in which deposition has a tendency tobecome unstable. In addition, a nitrogen-based gas mixing ratio ispreferably selected for the sputtering gas used in the high transmissionlayer formation step which is higher than the range of nitrogen-basedgas mixing ratios at which deposition is in the transition mode.

In the mask blank and method for manufacturing a mask blank of thepresent disclosure, the phase-shift film has a laminated structureconsisting of a low transmission layer and a high transmission layerinstead of a single layer structure. As a result of employing thislaminated structure, the low transmission layer can be deposited byreactive sputtering according to the region of the metal mode where afilm having a low nitrogen content tends to be formed, while the hightransmission layer can be deposited by reactive sputtering according tothe region of the reaction mode where a film having a high nitrogencontent tends to be formed. As a result, both the low transmission layerand the high transmission layer can be deposited by reactive sputteringaccording to deposition conditions in which fluctuations in depositionrate and voltage during deposition are small, and as a result thereof, aphase-shift film can be formed in which uniformity of composition andoptical characteristics is high and defectivity is low.

The low transmission layer and the high transmission layer are formedfrom a material consisting of silicon and nitrogen or a materialconsisting of silicon, nitrogen and one or more elements selected fromsemi-metallic elements, non-metallic elements and noble gas. The lowtransmission layer and the high transmission layer do not contain atransition metal that can cause a decrease in light fastness withrespect to ArF exposure light. In addition, the low transmission layerand the high transmission layer preferably do not contain a metalelement other than a transition metal. This is because the potential formetal elements other than transition metals to cause a decrease in lightfastness with respect to ArF exposure light cannot be ruled out. The lowtransmission layer and the high transmission layer may also contain anysemi-metallic element in addition to silicon. Among these semi-metallicelements, one or more elements selected from boron, germanium, antimonyand tellurium are preferably contained. Electrical conductivity of thesputtering target can be expected to be enhanced by the addition ofthese elements to the sputtering target.

The low transmission layer and the high transmission layer may alsocontain any non-metallic element in addition to nitrogen. Among thesenon-metallic elements, one or more elements selected from carbon,fluorine and hydrogen are preferably contained. The content of oxygen inthe low transmission layer and high transmission layer is preferably notmore than 10 at %, more preferably not more than 5 at %, and is evenmore preferably such that as little oxygen is contained as possible(such that the result of RBS, XPS or other composition analyses is belowthe detection limit). If oxygen is contained in the silicon-basedmaterial film, the extinction coefficient k tends to decreaseconsiderably and the overall thickness of the phase-shift film ends upbecoming excessively thick. The transparent substrate is typicallyformed from a material such as synthetic quartz glass having SiO₂ as amain component thereof. In the case either the low transmission layer orthe high transmission layer are formed in contact with the surface ofthe transparent substrate, the difference between the composition of thesilicon-based material film comprising oxygen and the composition of theglass becomes small if the silicon-based material film comprises oxygen.Consequently, the problem arises in which it becomes difficult to obtainetching selectivity between the silicon-based material film and thetransparent substrate during dry etching carried out when forming apattern on the phase-shift film.

One or more elements selected from boron, germanium, antimony andtellurium are preferably contained as a semi-metallic element in atarget composed of a material consisting one or more elements selectedfrom semi-metallic elements and non-metallic elements in silicon. Thisis because these semi-metallic elements can be expected to enhanceelectrical conductivity of the target. In the case of forming the lowtransmission layer and high transmission layer by DC sputtering inparticular, electrical conductivity of the target is preferably enhancedby containing these semi-metallic elements in the target.

The low transmission layer and the high transmission layer may alsocontain a noble gas. A noble gas is an element that is able to increasedeposition rate and improve productivity by being present in thedeposition chamber when depositing a thin film by reactive sputtering.Target constituent elements are scattered from the target as a result ofthe noble gas plasmifying and colliding with the target. The scatteredtarget constituent elements incorporate reactive gas during the courseof plasmification while being laminated on the transparent substrate toform a thin film. A slight amount of noble gas is incorporated in thedeposition chamber during the time from scattering of target constituentelements from the target through adhesion to the transparent substrate.Preferable examples of noble gases required by this reactive sputteringinclude argon, krypton and xenon. In addition, helium or neon, having alow atomic weight, can be aggressively incorporated into the thin filmin order to relax stress in the thin film.

In the low transmission layer formation step of forming the lowtransmission layer of a phase-shift film and the high transmission layerformation step of forming the high transmission layer, a nitrogen-basedgas is contained in the sputtering gas. Any nitrogen-based gas can beapplied for this nitrogen-based gas if it contains nitrogen. As waspreviously described, since it is preferable to reduce the oxygencontent in the low transmission layer and high transmission layer to alow level, an oxygen-free nitrogen-based gas is applied preferably, andnitrogen gas (N₂ gas) is applied more preferably.

The present disclosure is a method for manufacturing a mask blankprovided with a phase-shift film on a transparent substrate, thephase-shift film having a function to transmit ArF exposure lighttherethrough at a predetermined transmittance and generate apredetermined amount of phase shift in the ArF exposure light that istransmitted therethrough. The aforementioned phase-shift film comprisesa structure in which a low transmission layer and a high transmissionlayer are laminated. The method for manufacturing a mask blank of thepresent disclosure comprises a low transmission layer formation step anda high transmission layer formation step. The low transmission layerformation step comprises the formation of the aforementioned lowtransmission layer on or above the transparent substrate by reactivesputtering in a sputtering gas comprising a nitrogen-based gas and anoble gas using a silicon target or a target composed of a materialconsisting one or more elements selected from semi-metallic elements andnon-metallic elements in silicon. The high transmission layer formationstep comprises the formation of the high transmission layer on or abovethe transparent substrate by reactive sputtering in a sputtering gascomprising a nitrogen-based gas and a noble gas, and having a highermixing ratio of nitrogen-based gas than the aforementioned lowtransmission layer formation step, using a silicon target or a targetcomposed of a material consisting one or more elements selected fromsemi-metallic elements and non-metallic elements in silicon.

The low transmission layer and the high transmission layer in thephase-shift film preferably have a structure in which they are laminatedin mutual direct contact without interposing another film there between.In addition, the mask blank of the present disclosure preferably has afilm structure in which a film composed of a material containing a metalelement does not contact the low transmission layer or the hightransmission layer. This is because, if heat treatment of irradiationwith ArF exposure light is carried out in a state in which a filmcontaining a metal element is in contact with the film containingsilicon, the metal element tends to easily diffuse into the filmcontaining silicon.

The low transmission layer and the high transmission layer arepreferably composed of the same constituent elements. In the case eitherthe low transmission layer or the high transmission layer comprises adifferent constituent element, and heat treatment or irradiation withArF exposure light is carried out in a state in which they are laminatedwhile making contact, there is the risk of the different constituentelement migrating to and diffusing into a layer on a side not comprisingthe constituent element. There is then the risk of opticalcharacteristics of the low transmission layer and high transmissionlayer varying considerably from those at the time of initial deposition.In addition, in the case the different constituent element is asemi-metallic element in particular, the low transmission layer and thehigh transmission layer must be deposited using different targets.

In the mask blank of the present disclosure, examples of the material ofthe transparent substrate include, in addition to synthetic quartzglass, quartz glass, aluminosilicate glass, soda lime glass and lowthermal expansion glass (such as SiO₂—TiO₂ glass). Synthetic quartzglass demonstrates high transmittance with respect to ArF excimer laserlight (wavelength: 193 nm) and is particularly preferable as a materialused to form the transparent substrate of the mask blank.

The order in which the low transmission layer and the high transmissionlayer are laminated from the side of the transparent substrate in thephase-shift film may be any order. In the case of a phase-shift filmstructure in which the low transmission layer and the high transmissionlayer are laminated in that order in contact with the transparentsubstrate, there is the effect of more easily obtaining etchingselectivity between the low transmission layer and the transparentsubstrate formed from a material having SiO₂ as the main componentthereof since the low transmission layer is a silicon-containing filmhaving a low nitrogen content. In addition, when a pattern is formed ona silicon-containing film by dry etching, although a fluorine-based gasis typically used for the etching gas used in dry etching, achlorine-based gas can also be applied for the etching gas for asilicon-containing film having a low nitrogen content. Etchingselectivity between the low transmission layer and the transparentsubstrate can be enhanced considerably by using a chlorine-based gas fordry etching the low transmission layer.

On the other hand, in the case of a phase-shift film structure in whichthe high transmission layer and the low transmission layer are laminatedin that order in contact with the transparent substrate, the hightransmission layer is a silicon-containing film having a high nitrogencontent. Consequently, in the case the high transmission layer is formedin contact with the transparent substrate formed from a material havingSiO₂ as a main component thereof, there is the effect of easilyobtaining high adhesion between the surface of the transparent substrateand the high transmission layer.

The low transmission layer and the high transmission layer in thephase-shift film preferably have a structure in which they are laminatedin mutual direct contact without interposing another film there between.This is because a silicon-containing film is preferably not in a statein which it is in contact with a film composed of a material containingmetal elements for the reason previously described.

The phase-shift film preferably has two or more sets of a laminatedstructure composed of one layer of the low transmission layer and onelayer of the high transmission layer. In addition, the thickness of asingle layer of each of the low transmission layer and the hightransmission layer is preferably not more than 20 nm. The difference innitrogen content between films of the low transmission layer and hightransmission layer is large since their respective required opticalcharacteristics are different considerably. Consequently, there is alarge difference in etching rates during dry etching with afluorine-based gas between the low transmission layer and the hightransmission layer. In the case the phase-shift film employs a bilayerstructure composed of a single low transmission layer and a single hightransmission layer, when forming a pattern by dry etching using afluorine-based gas, level differences easily form in cross-sections ofthe pattern of the phase-shift film after etching. As a result of thephase-shift film employing a structure having two or more sets of alaminated structure consisting of a single low transmission layer and asingle high transmission layer, the thickness of each layer (singlelayer) of the low transmission layer and the high transmission layer canbe reduced in comparison with the case of the aforementioned bilayerstructure (containing one set of the laminated structure). Consequently,level differences forming in cross-sections of the pattern of thephase-shift film after etching can be decreased. In addition, as aresult of restricting the thickness of each layer (single layer) of thelow transmission layer and high transmission layer not to be more than20 nm, level differences forming in cross-sections of the pattern of thephase-shift film after etching can be further reduced.

In recent years, the correction of opaque defects, which occur duringfabrication of transfer masks (phase-shift masks) by forming a transferpattern on a mask blank thin film (phase-shift film) by dry etching, isincreasingly being carried out by defect correction using electron beamradiation (EB defect correction). This EB defect correction is atechnology in which thin films at portions containing opaque defects areremoved by converting to a volatile fluoride by irradiating portionscontaining opaque defects with an electron beam while gasifying asubstance such as XeF₂ in a non-excited state and supplying to thoseportions containing opaque defects. Since the XeF₂ or otherfluorine-based gas used in this EB defect correction has conventionallybeen supplied in a non-excited state, a thin film at those portions notirradiated with the electron beam was thought to be resistant to thoseeffects. However, it has been found that, in the case the thin film ofthe mask blank is formed with a silicon-based compound and the contentof oxygen or nitrogen in the silicon-based compound is low, that thinfilm ends up being etched by a fluorine gas such as XeF₂ in anon-excited state.

The low transmission layer of the phase-shift film in the presentdisclosure is a silicon-based material film that has a low nitrogencontent and does not include oxygen actively. Consequently, this lowtransmission layer tends to be easily etched by a fluorine-based gassuch as XeF₂ in a non-excited state during EB defect correction. Inorder to avoid etching of the low transmission layer, the lowtransmission layer is preferably placed in a state that makes itdifficult to contact the fluorine-based gas such as XeF₂ in anon-excited state. On the other hand, since the high transmission layeris formed with a silicon-based material having a high nitrogen content,it tends to be resistant to the effects of a fluorine-based gas such asXeF₂ in a non-excited state. As was previously described, as a result ofemploying a structure for the phase-shift film that has two or more setsof combinations of a laminated structure consisting of a lowtransmission layer and a high transmission layer, the low transmissionlayer is placed in a state in which it is either interposed between twohigh transmission layers or interposed between the transparent substrateand the high transmission layer. As a result, although there is apossibility of the low transmission layer initially being etched with afluorine-based gas such as XeF₂ in a non-excited state in contact with asidewall of the low transmission layer, it is subsequently difficult forthe fluorine-based gas in a non-excited state to contact the lowtransmission layer (since it is difficult for gas to enter as a resultof the surfaces of sidewalls of the low transmission layer being engagedby the surfaces of the sidewalls of the high transmission layer).Accordingly, as a result of adopting such a laminated structure, the lowtransmission layer can be inhibited from being etched by afluorine-based gas such as XeF₂ in a non-excited state. In addition, byrestricting the thickness of each layer of the low transmission layerand high transmission layer to be not more than 20 nm, the lowtransmission layer can be further inhibited from being etched by afluorine-based gas such as XeF₂ in a non-excited state. Furthermore, thethickness of the low transmission layer is preferably made to be lessthan the thickness of the high transmission layer.

The low transmission layer and the high transmission layer arepreferably formed from a material consisting of silicon and nitrogen. Inthe low transmission layer formation step of this method formanufacturing a mask blank, the low transmission layer is preferablyformed by reactive sputtering in a sputtering gas composed of nitrogenand a noble gas using a silicon target. In addition, in the hightransmission layer formation step, the high transmission layer ispreferably formed by reactive sputtering in a sputtering gas composed ofnitrogen and a noble gas using a silicon target.

As was previously described, containing a transition metal in the lowtransmission layer and high transmission layer can cause a decrease inlight fastness with respect to ArF exposure light. In the case ofcontaining a metal other than a transition metal or a semi-metallicelement other than silicon in the low transmission layer and the hightransmission layer, the metal or semi-metallic element contained has thepotential to change the optical characteristics of the low transmissionlayer and the high transmission layer accompanying migration between thelow transmission layer and the high transmission layer. In addition,transmittance with respect to ArF exposure light ends up decreasingconsiderably as a result of containing a non-metallic element in the lowtransmission layer and high transmission layer and further containingoxygen in the low transmission layer and high transmission layer. Inconsideration thereof, the low transmission layer and the hightransmission layer are preferably formed from a material containingsilicon and nitrogen. A noble gas is an element that is difficult to bedetected even in the case of carrying out a composition analysis such asRBS or XPS on the thin film. Consequently, a material further containinga noble gas can be considered to be included in the aforementionedmaterial containing silicon and nitrogen.

The low transmission layer is preferably formed from a material having arefractive index n with respect to ArF exposure light of less than 2.5(preferably not more than 2.4, more preferably not more than 2.2 andeven more preferably not more than 2.0) and the extinction coefficient kwith respect to ArF exposure light of not less than 1.0 (preferably notless than 1.1, more preferably not less than 1.4 and even morepreferably not less than 1.6). In addition, the high transmission layeris preferably formed from a material having a refractive index n withrespect to ArF exposure light of not less than 2.5 (preferably not lessthan 2.6) and the extinction coefficient of less than 1.0 (preferablynot more than 0.9, more preferably not more than 0.7 and even morepreferably not more than 0.4). In the case of composing a phase-shiftfilm with a laminated structure having two or more layers, therefractive indices n and extinction coefficients k of the lowtransmission layer and high transmission layer are required to each bewithin the aforementioned ranges. As a result, a phase-shift filmcomposed with a laminated structure having two or more layers is able todemonstrate characteristics required for use as a phase-shift film, orin other words, demonstrate the characteristics of having apredetermined phase difference and a predetermined transmittance withrespect to ArF exposure light.

The refractive index n and extinction coefficient k of a thin film arenot only determined by the composition of that thin film. Film densityand crystalline state of the thin film are also elements that have aneffect on the refractive index n and extinction coefficient k.Consequently, a thin film is deposited so as to have a desiredrefractive index n and extinction coefficient k by adjusting variousconditions when depositing the thin film by reactive sputtering.Although the ratio of a mixed gas of a noble gas and reactive gas can beadjusted when depositing the low transmission layer and the hightransmission layer by reactive sputtering in order to make therefractive index n and the extinction coefficient k to be within theaforementioned ranges, adjustment is not limited thereto. There are adiverse range of deposition conditions that have an effect on refractiveindex n and extinction coefficient k, examples of which include pressurewithin the deposition chamber when depositing by reactive sputtering,electrical power applied to the target, and the positional relationshipbetween the target and the transparent substrate such as the distancethere between. In addition, it is necessary to optimize these depositionconditions corresponding to each individual deposition apparatus andmake suitable adjustments so that the thin film formed demonstrates thedesired refractive index n and extinction coefficient k.

The phase-shift film is preferably provided with an uppermost layer at aposition farthest away from the transparent substrate, and the uppermostlayer is formed from a material consisting of silicon, nitrogen andoxygen, or a material consisting of silicon, nitrogen, oxygen and one ormore elements selected from semi-metallic elements, non-metallicelements and noble gases. In addition, this method for manufacturing amask blank preferably has an uppermost layer formation step of formingan uppermost layer at a position of the phase-shift film farthest awayfrom the transparent substrate by sputtering in a sputtering gascomprising a noble gas using a silicon target or a target composed of amaterial consisting one or more elements selected from semi-metallicelements and non-metallic elements in silicon. Moreover, this method formanufacturing a mask blank more preferably has an uppermost layerformation step of forming an uppermost layer at a position of theaforementioned phase-shift film farthest away from the transparentsubstrate by reactive sputtering in a sputtering gas composed ofnitrogen gas and a noble gas using a silicon target, and carrying outtreatment in which at least the surface layer of the aforementioneduppermost layer is oxidized.

Although a silicon-based material containing nitrogen while notcontaining oxygen actively demonstrates high light fastness with respectto ArF exposure light, chemical resistance tends to be low in comparisonwith a silicon-based material film containing oxygen actively. Inaddition, in the case of a mask blank having a configuration in whichthe uppermost layer is provided on the opposite side of the phase-shiftfilm from the side of the transparent substrate, and a high transmissionlayer or low transmission layer that contains nitrogen but does notcontain oxygen actively is arranged thereon, the surface layer of thephase-shift film is oxidized and it is difficult to avoid oxidation as aresult of carrying out mask cleaning on a phase-shift mask fabricatedfrom this mask blank and storing in air. Optical characteristics of aphase-shift film end up varying greatly from optical characteristics atthe time of thin film deposition due to oxidation of the surface layerof the phase-shift film. In the case of a configuration in which a lowtransmission layer is provided as the uppermost layer of a phase-shiftfilm in particular, the amount of the increase in transmittance ends upbecoming large due to oxidation of the low transmission layer. Surfaceoxidation of the low transmission layer and high transmission layer canbe inhibited by employing a structure in which the phase-shift film isfurther provided with an uppermost layer, formed from a materialcomposed of silicon, nitrogen and oxygen or a material containing one ormore elements selected from semi-metallic elements, non-metallicelements and noble gases in the material composed of silicon, nitrogenand oxygen, on a laminated structure consisting of a low transmissionlayer and high transmission layer.

An uppermost layer formed from a material composed of silicon, nitrogenand oxygen or a material containing one or more elements selected fromsemi-metallic elements, non-metallic elements and noble gases in thematerial composed of silicon, nitrogen and oxygen can have aconfiguration in which the composition is nearly the same in thedirection of layer thickness or can have a configuration having acomposition gradient in the direction of layer thickness (configurationin which the uppermost layer has a composition gradient in which layeroxygen content increases moving away from the transparent substrate).Examples of materials that are preferable for the uppermost layer with aconfiguration in which the composition is nearly the same in thedirection of layer thickness include SiO₂ and SiON. The uppermost layerwith a configuration in which there is a composition gradient in thedirection of layer thickness is preferably that in which SiN is on theside of the transparent substrate, oxygen content increases moving awayfrom the transparent substrate, and the surface layer is SiO₂ or SiON.

An uppermost layer formation step can be applied to form the uppermostlayer in which the uppermost layer is formed by reactive sputtering in asputtering gas comprising nitrogen gas, oxygen gas and noble gas using asilicon target or a target composed of a material consisting one or moreelements selected from semi-metallic elements and non-metallic elementsin silicon. This uppermost layer formation step can be applied to boththe formation of an uppermost layer with a configuration in which thecomposition is nearly the same in the direction of layer thickness andthe formation of an uppermost layer with a configuration having acomposition gradient. In addition, an uppermost layer formation step canbe applied to form an uppermost layer in which the uppermost layer isformed by sputtering in a sputtering gas comprising a noble gas using asilicon dioxide (SiO₂) target or a target composed of a materialconsisting one or more elements selected from semi-metallic elements andnon-metallic elements in silicon dioxide (SiO₂). This uppermost layerformation step can also be applied to both the formation of an uppermostlayer with a configuration in which the composition is nearly the samein the direction of layer thickness and the formation of an uppermostlayer with a configuration having a composition gradient.

An uppermost layer formation step can be applied to form the uppermostlayer in which the uppermost layer is formed by reactive sputtering in asputtering gas comprising nitrogen gas and noble gas using a silicontarget or a target composed of a material consisting one or moreelements selected from semi-metallic elements and non-metallic elementsin silicon, and treatment is further carried out in which at least thesurface layer of this uppermost layer is oxidized. This uppermost layerformation step can be applied to the formation of the uppermost layerbasically having a composition gradient in the direction of layerthickness. Examples of treatment used to oxidize the surface layer ofthe uppermost layer in this case include heat treatment in a gas such asair that contains oxygen and contacting ozone or oxygen plasma with theuppermost layer.

Although the low transmission layer, high transmission layer anduppermost layer in the phase-shift film are formed by sputtering, anytype of sputtering, such as DC sputtering, RF sputtering or ion beamsputtering, can be applied. In the case of using a target having lowelectrical conductivity (such as a silicon target or silicon compoundtarget that does not contain or only contains a small amount of asemi-metallic element), RF sputtering or ion beam sputtering is appliedpreferably. In consideration of deposition rate, RF sputtering isapplied more preferably in the case of using a target having lowelectrical conductivity.

In each of the steps for forming the low transmission layer and hightransmission layer of the phase-shift film by sputtering, sputtering canbe applied both in the case of forming the low transmission layer andhigh transmission layer in the same deposition chamber and in the caseof forming in different deposition chambers. In addition, in the case offorming the low transmission layer and the high transmission layer inthe same deposition chamber, although there are cases in which the lowtransmission layer and high transmission layer are formed with the sametarget and cases in which they are formed with different targets,sputtering can be applied in either case. Furthermore, in the case offorming the low transmission layer and the high transmission layer indifferent deposition chambers, a configuration is preferably employed inwhich each deposition chamber is linked through different vacuumchambers. In this case, a load-lock chamber, through which a transparentsubstrate exposed to air passes when introduced into the vacuum chamber,is preferably linked to the vacuum chamber. In addition, a transportapparatus (robot hand) for transporting the transparent substrate ispreferably provided between the load-lock chamber, vacuum chamber andeach deposition chamber.

In order to allow the phase-shift effect thereof to functioneffectively, transmittance with respect to ArF exposure light of thephase-shift film in the mask blank of the present disclosure ispreferably not less than 1% and more preferably not less than 2%. Inaddition, transmittance with respect to ArF exposure light of thephase-shift film is preferably adjusted to be not more than 30%, morepreferably not more than 20% and even more preferably not more than 18%.In addition, in the phase-shift film, the phase difference generatedbetween ArF exposure light that transmits through the phase-shift filmand light that has transmitted through air over the same distance as thethickness of the phase-shift film is preferably adjusted to be withinthe range of 170 degrees to 190 degrees.

In the mask blank of the present disclosure, a light shielding film ispreferably laminated on the phase-shift film. In general, the outerperipheral region of the region where a transfer pattern is formed in atransfer mask (transfer pattern formation region) is required to securean optical density (OD) equal to or greater than a predetermined value.This is to prevent a resist film from being affected by exposure lightthat has transmitted through the outer peripheral region during exposureof the resist film on a semiconductor wafer using an exposure apparatus.This applies similarly in the case of a phase-shift mask. Normally, inthe outer peripheral region of a transfer mask comprising a phase-shiftmask, the OD thereof is preferably not less than 3.0 and required to benot less than at least 2.8. As was previously described, the phase-shiftfilm has a function to transmit exposure light therethrough at apredetermined transmittance, and it is difficult to secure opticaldensity equal to or greater than a predetermined value with aphase-shift film alone. Consequently, a light shielding film ispreferably laminated on the phase-shift film at the stage ofmanufacturing the mask blank in order to compensate for the deficientoptical density. As a result of employing this configuration for themask blank, a phase-shift mask can be manufactured that secures apredetermined value of optical density for the outer peripheral regionif the light shielding film of a region that uses phase-shift effects(basically the transfer pattern formation region) is removed at anintermediate point in the manufacturing of the phase-shift film.

The light shielding film can be applied to a single layer structure or alaminated structure having two layers or more. In addition, each layerof the light shielding film having a single layer structure or lightshielding film having a laminated structure of two layers or more mayhave a configuration in which the composition is nearly the same in thedirection of film or layer thickness or may have a configuration inwhich there is a composition gradient in the direction of layerthickness.

In the case of not interposing another film between the light shieldingfilm and the phase-shift film, a material is required to be applied forthe light shielding film that has adequate etching selectivity withrespect to the etching gas used when forming a pattern on thephase-shift film. In this case, the light shielding film is preferablyformed from a material containing chromium. Examples of materialscontaining chromium used to form this light shielding film includechromium metal as well as materials containing chromium and one or moreelements selected from oxygen, nitrogen, carbon, boron and fluorine. Ingeneral, although chromium-based materials are etched with a mixed gasof a chlorine-based gas and oxygen gas, the etching rate of chromiummetal with respect to this etching gas is not very high. Inconsideration of enhancing etching rate with respect to an etching gasconsisting of a mixed gas of a chlorine-based gas and oxygen gas, amaterial containing chromium and one or more elements selected fromoxygen, nitrogen, carbon, boron and fluorine is preferably used for thematerial used to form the light shielding film. In addition, one or moreelements among molybdenum, indium and tin may also be contained in thematerial containing chromium used to form the light shielding film.Etching rate with respect to a mixed gas of a chlorine-based gas andoxygen gas can be further enhanced by containing one or more of theelements of molybdenum, indium and tin.

On the other hand, in the mask blank of the present disclosure, in thecase of employing a configuration in which another film is interposedbetween the light shielding film and the phase-shift film, aconfiguration is preferably employed in which the other film(combination of etching stopper and etching mask film) is formed from amaterial containing the aforementioned chromium and the light shieldingfilm is formed from a material containing silicon. Although materialscontaining chromium are etched by a mixed gas of a chlorine-based gasand oxygen gas, a resist film formed with an organic material is easilyetched by this mixed gas. A material containing silicon is typicallyetched with a fluorine-based gas or chlorine-based gas. Since theseetching gases basically do not contain oxygen, the etched amount of aresist film formed with an organic material can be reduced to a greaterdegree than in the case of etching with a mixed gas of a chlorine-basedgas and oxygen gas. Consequently, film thickness of the resist film canbe reduced.

A transition metal may be contained or a metallic element other than atransition metal may be contained in the material containing siliconthat is used to form the light shielding film. This is because, in thecase of fabricating a phase-shift mask from this mask blank, thecumulative amount irradiated with ArF exposure light is low incomparison with the transfer pattern formation region since the patternin which the light shielding film is formed is basically a pattern of alight shielding band around the outer periphery, and because it isunlikely for any substantial problems to occur even if fastness to ArFlight is low since this light shielding film rarely remains in a finepattern. In addition, in the case a transition metal is contained in thelight shielding film, light shielding performance of the light shieldingfilm is greatly improved in comparison with the case of not containing atransition metal, thereby making it possible to reduce the thickness ofthe light shielding film. Examples of transition metals contained in thelight shielding film include a metal such as molybdenum (Mo), tantalum(Ta), tungsten (W), titanium (Ti), chromium (Cr), hafnium (Hf), nickel(Ni), vanadium (V), zirconium (Zr), ruthenium (Ru), rhodium (Rh),niobium (Nb) and palladium (Pd), and alloys of these metals.

The light shielding film may be formed from a material that containstantalum (Ta) and one or more elements selected from hafnium (Hf) andzirconium (Zr), but does not contain oxygen with the exception of thesurface layer thereof. The light shielding film in this case can be dryetched with an etching gas that contains a chlorine-based gas but doesnot contain oxygen gas, and has etching selectivity with the materialthat forms the phase-shift film with respect to dry etching with anetching gas containing a fluorine-based gas.

When considering the aforementioned etching characteristics, the lightshielding film is more preferably formed with a tantalum-hafnium alloy,tantalum-zirconium alloy, tantalum-hafnium-zirconium alloy or compoundcontaining these alloys along with an element other than oxygen.Examples of elements other than oxygen contained in the light shieldingfilm in this case include nitrogen (N), carbon (C), hydrogen (H), boron(B) and the like. In addition, the material of the light shielding filmin this case may also comprise an inert gas such as helium (He), argon(Ar), krypton (Kr) or xenon (Xe). Furthermore, the material of the lightshielding film in this case is a material that can be dry-etched with anetching gas that contains a chlorine-based gas but does not containoxygen gas, and it is difficult for this etching gas to etch thephase-shift film.

In a mask blank provided with a light shielding film by laminating ontothe aforementioned phase-shift film, a configuration is more preferablyemployed in which an etching mask film, which is formed from a materialhaving etching selectivity with respect to the etching gas used whenetching the light shielding film, is further laminated on the lightshielding film. Since the light shielding film is required to have afunction that secures a predetermined optical density, there arelimitations on the degree to which the thickness thereof can be reduced.The etching mask film is only required to have a film thickness thatenables it to function as an etching mask until completion of dryetching for forming a pattern in the light shielding film directly therebelow, and is basically not subject to any optical restrictions.Consequently, the thickness of the etching mask film can be greatlyreduced in comparison with the thickness of the light shielding film.Since a resist film of an organic material is only required to have afilm thickness that allows the resist film to function as an etchingmask until completion of dry etching for forming a pattern in thisetching mask film, the thickness of the resist film can also be greatlyreduced in comparison with the prior art.

In the case the light shielding film is formed from a materialcontaining chromium, the etching mask film is preferably formed with theaforementioned material containing silicon. Furthermore, since theetching mask film in this case tends to have low adhesion with theresist film of an organic material, surface adhesion is preferablyimproved by treating the surface of the etching mask film withhexamethyldisilazane (HMDS). Furthermore, the etching mask film in thiscase is preferably formed with, for example, SiO₂, SiN, SiON or thelike. In addition to the previously described materials, a materialcontaining tantalum can be applied for the material of the etching maskfilm in the case the light shielding film is formed from a materialcontaining chromium. Examples of materials containing tantalum in thiscase include tantalum metal as well as materials containing tantalum andone or more elements selected from nitrogen, oxygen, boron and carbon.Examples of those materials include Ta, TaN, TaON, TaBN, TaBON, TaCN,TaCON, TaBCN and TaBOCN. On the other hand, in the case the lightshielding film is formed from a material containing silicon, thisetching mask film is preferably formed with the aforementioned materialscontaining chromium.

In the mask blank of the present disclosure, an etching stopper filmcomposed of material having etching selectivity for both the transparentsubstrate and the phase shift-film (such as the aforementioned materialscontaining chromium, examples of which include Cr, CrN, CrC, CrO, CrONand CrC) may be formed between the transparent substrate and thephase-shift film.

In the mask blank of the present disclosure, a resist film of an organicmaterial is preferably formed in contact with the surface of theaforementioned etching mask film at a film thickness of not more than100 nm. In the case of a fine pattern corresponding to the DRAM hp32 nmgeneration, a sub-resolution assist feature (SRAF) having a line widthof 40 nm may be provided on the transfer pattern (phase-shift pattern)to be formed on the etching mask film. However, in this case as well,since the cross-sectional aspect ratio of the resist pattern can be madeto be low at 1:2.5, destruction or desorption of the resist pattern canbe inhibited when developing or rinsing the resist film. Furthermore,the film thickness of the resist film is more preferably not more than80 nm.

The phase-shift mask of the present disclosure is characterized in thata transfer pattern is formed on a phase-shift film of the aforementionedmask blank. In addition, the method for manufacturing a phase-shift maskof the present disclosure is characterized in that it has a step offorming a transfer pattern on a phase-shift film of a mask blankmanufactured according to the aforementioned manufacturing method. Thephase-shift mask of the present disclosure makes it possible to omittreatment for improving ArF light fastness after having formed a patternon the phase-shift film since the material per se that composes thephase-shift film is a material having high light fastness with respectto ArF exposure light.

FIG. 1 is a cross-sectional view showing the configuration of oneembodiment of the present disclosure in the form of a mask blank 100.This mask blank 100 employs a configuration in which a phase-shift film2, obtained by laminating a low transmission layer 21, a hightransmission layer 22 and an uppermost layer 23 in that order, a lightshielding film 3 and an etching mask film 4 are laminated on atransparent substrate 1. On the other hand, FIG. 2 is a cross-sectionalview showing the configuration of another embodiment of the presentdisclosure in the form of a mask blank 101. This mask blank 101 employsa configuration in which a phase-shift film 2, obtained by laminating ahigh transmission layer 22, a low transmission layer 21, the hightransmission layer 22, the low transmission layer 21 and an uppermostlayer 23 in that order, a light shielding film 3 and an etching mask 4are laminated on the transparent substrate 1. Details regarding eachconfiguration of the mask blank 100 and the mask blank 101 are aspreviously described. The following provides an explanation of oneexample of the method for manufacturing a phase-shift mask of thepresent disclosure in accordance with the manufacturing process shown inFIGS. 3A-3F. Furthermore, in this example, a material containingchromium is applied for the light shielding film, and a materialcontaining silicon is applied for the etching mask film.

First, a resist film was formed in contact with the etching mask film 4in the mask blank 100 by spin coating. Next, a transfer pattern to beformed on a phase-shift film (phase-shift pattern) in the form of afirst pattern was exposed and drawn on the resist film followed byfurther carrying out a predetermined treatment such as developmenttreatment to form a first resist pattern 5 a having a phase-shiftpattern (see FIG. 3A). Continuing, dry etching using a fluorine-basedgas was carried out using the first resist pattern 5 a as a mask to forma first pattern on the etching mask film 4 (etching mask pattern 4 a)(see FIG. 3B).

Next, after removing the resist pattern 5 a, dry etching using a mixedgas of a chlorine-based gas and oxygen gas was carried out using theetching mask pattern 4 a as a mask to form the first pattern on thelight shielding film 3 (light shielding film pattern 3 a) (see FIG. 3C).Continuing, dry etching using a fluorine-based gas was carried out usingthe light shielding pattern 3 a as a mask to form the first pattern onthe phase-shift film 2 (phase-shift pattern 2 a) while simultaneouslyremoving the etching mask pattern 4 a (see FIG. 3D).

Next, a resist film was formed on the mask blank 100 by spin coating.Next, a pattern to be formed on the light shielding film (lightshielding pattern) in the form of a second pattern was exposed anddeveloped on the resist film followed by further carrying out apredetermined treatment such as development treatment to form a secondresist pattern 6 b having a light shielding pattern. Continuing, dryetching using a mixed gas of a chlorine-based gas and oxygen gas wascarried out using the second resist pattern 6 b as a mask to form thesecond pattern on the light shielding film 3 (light shielding pattern 3b) (see FIG. 3E). Moreover, a phase-shift mask 200 was obtained byremoving the second resist pattern 6 b and going through predeterminedtreatment such as cleaning (see FIG. 3F).

There are no particular limitations on the aforementioned chlorine-basedgas used in the dry etching if it comprises Cl. Examples ofchlorine-based gases include Cl₂, SiCl₂, CHCl₃, CH₂Cl₂, CCl₄, BCl₃ andthe like. In addition, there are no particular limitations on theaforementioned fluorine-based gas used in the dry etching if itcomprises F. Examples of fluorine-based gases include CHF₃, CF₄, C₂F₆,C₄F₈, SF₆ and the like. Since fluorine-based gases not comprising C inparticular have a comparatively low etching rate with respect to glasssubstrates, the damage to glass substrates can be further decreased.

The phase-shift mask of the present disclosure is able to suppresschanges in CD (thickness) of a phase-shift pattern to within a smallrange even after having been cumulatively irradiated with exposure lightof an ArF excimer laser. Consequently, even if this phase-shift maskafter cumulative irradiation is placed on the mask stage of an exposureapparatus using an ArF excimer laser for exposure light, and aphase-shift pattern is exposed and transferred to a resist film on asemiconductor device, a pattern can be transferred to the resist film onthe semiconductor device at a level of precision that adequatelysatisfies design specifications.

Moreover, the method for manufacturing a semiconductor device of thepresent disclosure is characterized in that a pattern is exposed andtransferred to a resist film on a semiconductor substrate using theaforementioned phase-shift mask or a phase-shift mask manufactured usingthe aforementioned mask blank. Since the phase-shift mask and mask blankof the present disclosure have the previously described effects, even ifthe phase-shift mask of the present disclosure is placed on the maskstage of an exposure apparatus using an ArF excimer laser for exposurelight after having been cumulatively irradiated with exposure light ofan ArF excimer laser, and a phase-shift pattern is exposed andtransferred to a resist film on a semiconductor device, a pattern can betransferred to the resist film on the semiconductor device at a level ofprecision that adequately satisfies design specifications. Consequently,in the case of forming a circuit pattern by dry etching a lower layerfilm using the pattern of this resist film as a mask, a highly precisecircuit pattern can be formed that is free of wiring short-circuits anddisconnections attributable to inadequate precision.

Second Embodiment

The following provides an explanation of a second embodiment of thepresent disclosure.

As was previously described, in the case of forming a thin film byreactive sputtering, two stable sputtering modes appear corresponding tothe flow rate of the reactive gas. These two modes consist of a metalmode, in which the target surface is sputtered in the state of thetarget material, and a poison mode, in which the target surface issputtered in a state in which it has reacted with the reactive gas. Incomparison with the metal mode, the poison mode has a higher cathodevoltage applied to the target and a slower deposition rate.Consequently, when the flow rate of reactive gas in the sputtering gasis increased or decreased, the cathode applied voltage and depositionrate change rapidly at a certain flow rate and an unstable transitionoccurs between the metal mode and the poison mode. Moreover, the valueof the flow rate of the reactive gas when this transition occurs differsbetween when the flow rate increases (I in FIG. 4) and when it decreases(D in FIG. 4), and hysteresis (phenomenon in which the curve of flowrate when it is increasing does not coincide with the curve when it isdecreasing) occurs when the relationship between reactive gasconcentration and deposition rate are represented graphically (FIG. 4).If a film is deposited at a reactive gas flow rate that corresponds tothe range of hysteresis, the voltage applied to the target anddeposition rate become unstable, thereby preventing the formation of afilm having stable physical properties.

As described in Patent Literature 3, in the case of depositing a film ofa silicon compound on a substrate by reactive sputtering using a silicontarget having silicon as the target material thereof, a film having ahigh ratio of silicon comprising the film composition is deposited whenin the metal mode, and a film of a silicon compound in which the amountof silicon is close to the stoichiometric ratio is deposited when in thepoison mode. For example, in the formation of a phase-shift film of ahalftone phase-shift mask for use with an ArF excimer laser (wavelengthλ=193 nm), in the case of depositing silicon nitride on a mask blanksubstrate, if the silicon nitride is deposited in the metal mode havinga low flow rate of nitrogen gas for the reactive gas, a film is formedthat has a large extinction coefficient (k). Consequently, a phase-shiftfilm deposited in the metal mode substantially prevents the obtaining ofinterference effects and the like based on a phase difference sincetransmittance ends up being excessively low.

On the other hand, when a film is deposited in the poison mode having ahigh flow rate of nitrogen gas for the reactive gas, a film is formed onthe substrate that has a low extinction coefficient (k). Consequently, aphase-shift film deposited in the poison mode is unable to obtain therequired light fastness due to transmittance being excessively high. Inorder to obtain the function of a phase-shift mask, the phase-shift filmis required to have an extinction coefficient (k) that is intermediateto that of a film deposited in the poison mode and a film deposited inthe metal mode. However, there is the problem or having to deposit thefilm at a gas flow rate in an unstable transition state in order toobtain such a film having an intermediate extinction coefficient (k).

In this second embodiment, an aspect is to provide a method formanufacturing a mask blank that is able to solve the aforementionedproblem as well as problems to be subsequently described that occur inrelation thereto. In addition, in this second embodiment, an aspect isto provide a method for manufacturing a mask blank that demonstrateshigh uniformity of composition and optical characteristics of aphase-shift film in the in-plane direction and direction of thickness,demonstrates high uniformity of composition and optical characteristicsof the phase-shift film between a plurality of substrates, and has lowdefectivity in a mask blank provided with a phase-shift film on atransparent substrate even in the case of applying a silicon-basedmaterial not containing a transition metal for the phase-shift film. Inaddition, an aspect is to provide a method for manufacturing aphase-shift mask manufactured using a mask blank obtained according tothis manufacturing method.

This disclosure of the second embodiment has the followingconfigurations in order to achieve the aforementioned aspects.

(Configuration 1A)

A method for manufacturing a mask blank having a step of forming aphase-shift film having a laminated structure on a transparent substrateby sputtering by introducing an inert gas and a reactive gas into avacuum chamber, wherein the aforementioned step of forming a phase-shiftfilm has:

a step of arranging two or more targets at least comprising silicon inthe vacuum chamber and forming a low transmission layer by sputteringone of the aforementioned targets in a metal mode, and

a step of forming a high transmission layer by sputtering the other ofthe aforementioned targets in a poison mode; and comprises a step offorming a phase-shift film having a laminated structure in which the lowtransmission layer and high transmission layer are laminated in anyorder by these steps.

(Configuration 2A)

The method for manufacturing a mask blank described in Configuration 1A,wherein the reactive gas is a gas in which the reactive gas introducedduring formation of the low transmission layer and the reactive gasintroduced during formation of the high transmission layer are the sametype of gas.

(Configuration 3A)

The method for manufacturing a mask blank described in Configuration 1Aor Configuration 2A, wherein the target material is silicon.

(Configuration 4A)

The method for manufacturing a mask blank described in any ofConfigurations 1A to 3A, wherein the reactive gas is nitrogen gas.

(Configuration 5A)

The method for manufacturing a mask blank described in any ofConfigurations 1A to 4A, wherein the low transmission layer is formed asa layer having a refractive index n with respect to exposure light of anArF excimer laser of less than 2.4 and has an extinction coefficient kof not less than 1.0, and

the high transmission layer is formed as a layer having a refractiveindex n with respect to exposure light of an ArF excimer laser of notless than 2.4 and has an extinction coefficient k of less than 1.0.

(Configuration 6A)

The method for manufacturing a mask blank described in any ofConfigurations 1A to 5A, wherein the laminated structure in which thelow transmission layer and the high transmission layer are laminated inany order is formed by alternately laminating three or more layers ofthe low transmission layer and the high transmission layer.

(Configuration 7A)

The method for manufacturing a mask blank described in any ofConfigurations 1A to 6A, wherein the method for manufacturing a maskblank of the present disclosure comprises forming an oxidized layer onthe surface of the phase-shift film having a laminated structure inwhich the low transmission layer and the high transmission layer arelaminated in any order.

(Configuration 8A)

A method for manufacturing a phase-shift mask, comprising forming atransfer pattern in the phase-shift film of a mask blank manufacturedusing the method for manufacturing a mask blank of any of Configurations1A to 7A.

According to the method for manufacturing a mask blank according to eachof configuration of the aforementioned second embodiment, a mask blankcan be manufactured in which uniformity of the composition and opticalproperties of a phase-shift film in the in-plane direction and directionof film thickness can be made to be high, uniformity of the compositionand optical characteristics of the phase-shift film between a pluralityof substrates can also be made to be high, and defectivity can be madeto be low. In addition, a phase-shift mask having superiortransferability can be obtained by manufacturing a phase-shift maskusing a mask blank manufactured according to the method formanufacturing a mask blank in each configuration of the aforementionedsecond embodiment.

In each configuration of the aforementioned second embodiment, the“target material” is that which comprises silicon and there are nolimitations on the presence or absence of other components. A materialcomprising silicone can be suitably selected and used for the targetmaterial used to deposit the phase-shift film of a halftone phase-shiftmask. Examples of targets used for the phase-shift film include asilicon target and mixed targets comprising silicon. Examples of “mixedtargets comprising silicon” as referred to here include mixed targetscomposed of silicon and a transition metal (such as silicon andmolybdenum). Examples of transition metals present in mixed targetscomposed of silicon and a transition metal include molybdenum, tantalum,tungsten, titanium, hafnium, nickel, vanadium, zirconium, niobium,palladium, ruthenium, rhodium and chromium. A target that is preferablyapplied in the second embodiment is a silicon target or a mixed targetcomprising silicon, and a target that is more preferably applied is asilicon target.

Furthermore, in this second embodiment, “silicon” of the target materialrefers to that substantially composed of silicon. A silicon target inwhich the surface has undergone natural oxidation, a silicon targetcomprising impurity elements introduced during manufacturing of thetarget, and a silicon target comprising components such as elementsadded for the purpose of stabilization or improving sputteringefficiency and the like are included in the concept of a targetcontaining “silicon” as a material thereof as referred to here. Inaddition, examples of elements added for the purpose of improvingsputtering efficiency include boron, germanium, antimony and tellurium.Since a silicon target to which these elements have been added maintainsa high level of electrical conductivity of the target surface duringsputtering, they are used preferably in the case of depositing a film byDC sputtering.

In each configuration of the aforementioned second embodiment, the “twotargets” may both contain silicon or may be targets in which thecontents of silicon and the contents of other elements contained otherthan silicon may be different from each other. For example, a mixedtarget of a metal and silicon may be used for the target used in themetal mode, a silicon target may be used for the target used in thepoison mode, and the targets may be arranged in a chamber. In addition,in the case of using silicon targets for the two targets, a substancethat imparts electrical conductivity may be added only to the silicontarget used in the poison mode.

In a film formed by sputtering these target materials, opticalcharacteristics in the form of the extinction coefficient and refractiveindex of the film deposited in the metal mode and the film deposited inthe poison mode are mutually different. For example, by preparing aplurality of targets composed of the same material, using the targetsseparately for the poison mode and the metal mode, and laminating filmsdeposited in each mode in any order, a thin film having a laminatedstructure can be deposited that has desired optical characteristics.

In each configuration of the aforementioned second embodiment, the“reactive gas” may be a reactive gas typically used in reactivesputtering for depositing a film composed of a reaction product byreacting with a target material, and there are no limitations on thespecific type of gas. Specific examples of reactive gases includenitrogen, oxygen, nitrogen oxide, methane and carbon dioxide.

In each configuration of the aforementioned second embodiment, examplesof gases able to be used as an “inert gas” include noble gases such ashelium, argon, krypton or xenon. Constituent elements are scattered fromthe target and react with the reactive gas by plasmifying the inert gasand causing it to collide with the target. The reaction product of thereactive gas and target constituent elements is deposited on atransparent substrate in the form of a thin film.

In each configuration of the aforementioned second embodiment, examplesof the “transparent substrate” include, in addition to synthetic quartzglass, quartz glass, aluminosilicate glass, soda lime glass and lowthermal expansion glass (such as SiO₂—TiO₂ glass). Synthetic quartzglass is particularly preferably as a material that forms thetransparent substrate of a mask blank due to its high transmittance withrespect to an ArF excimer laser (wavelength: 193 nm).

In each configuration of the aforementioned second embodiment, DCsputtering or RF sputtering can be applied for the “sputtering” method.In the case of using a silicon target or mixed target comprising siliconhaving low electrical conductivity, RF sputtering is applied preferably.RF sputtering is also applied preferably in the case of consideringdeposition rate.

The lamination order of the low transmission layer and high transmissionlayer of the phase-shift film from the side of the transparent substratein each configuration of the aforementioned second embodiment is suchthat the layer that is more preferable based on correlationcharacteristics between the transparent substrate and the layer incontact therewith is formed as the layer on the side of the transparentsubstrate, and either layer may be formed first. For example, when thelow transmission layer allows the obtaining of etching selectivity witha substrate to a greater degree than the high transmission layer, thelow transmission layer is selected for use as the layer that contactsthe substrate. In addition, in the case the high transmission layerdemonstrates superior adhesion with the substrate in comparison with thelow transmission layer, the high transmission layer can be selected foruse as the layer that contacts the substrate.

One characteristic of each configuration of the aforementioned secondembodiment is that at least two or more targets containing silicon arearranged in a row, and the targets are used separately as a targetdeposited with a film in the metal mode and a target deposited with afilm in the poison mode. Accordingly, regardless of which of the lowtransmission layer and high transmission layer is deposited, sputteringoccurs on only one of the targets. When voltage is applied to one of thetargets, voltage is not applied to the other target.

In the case of using deposition in the metal mode and deposition in thepoison mode with the same target, it is necessary to carefully conditionthe target prior to changing the physical properties (mode) of thetarget surface. However, target conditioning is a process that causesthe generation of contaminants in the vacuum chamber. Contaminants are acause of film defects. Specific examples of these contaminants includecontaminants that precipitate on the target surface when the modechanges, and contaminants generated by mechanical operation of a shutterand the like that is used during conditioning. In consideration of thesecontaminants, the number of times the target is subjected toconditioning is preferably as low as possible in order to manufacture amask blank having low defectivity.

According to each configuration of the aforementioned second embodiment,since a target deposited with a film in the metal mode and a targetdeposited with a film in the poison mode are used separately, frequentconditioning of the targets is not required accompanying a change in themode. According to the second embodiment, the generation of contaminantsas in the previously described example during formation of a phase-shiftfilm can be effectively inhibited. Thus, a mask blank having lowdefectivity can be manufactured in which the number of defectsattributable to contaminants is low.

In addition, one characteristic of the manufacturing method in eachconfiguration of the aforementioned second embodiment is that the lowtransmission layer is deposited in the metal mode and the hightransmission layer is deposited in the poison mode. Since reactivesputtering can be carried out stably when the target is in the poisonmode and when the target is in the metal mode, uniformity of compositionand optical characteristics in the in-plane direction and direction ofthickness of the phase-shift film can be made to be high, and uniformityof composition and optical characteristics of the phase-shift filmbetween a plurality of substrates can also be made to be high. Moreover,there is also the effect of increasing the degree of freedom of opticaldesign of the phase-shift film by combining the layer deposited in thepoison mode and the layer deposited in the metal mode and adjusting thethickness of each layer.

In the method for manufacturing a mask blank according to theaforementioned second embodiment, the aforementioned reactive gas issuch that the reactive gas introduced during formation of the lowtransmission layer and the reactive gas introduced during formation ofthe high transmission layer are preferably the same type of gas. Namely,the aforementioned reactive gas is preferably the same type of gas whenforming the low transmission layer and when forming the hightransmission layer.

In the case the type of reactive gas is the same in the case ofdepositing a film in the poison mode and the case of depositing a filmin the metal mode, constituent elements of the high transmission layerobtained in the poison mode and constituent elements of the lowtransmission layer obtained in the metal mode are the same. Thus, sidereactions such as exchange reactions occurring at the interface betweenthe high transmission layer and low transmission layer do not becomecomplex. Consequently, even in the case of a film having a laminatedstructure, the overall composition of the film is kept uniform andunexpected changes in phase-shift function are unlikely to occur.Furthermore, in the present configuration, only the reactive gasintroduced when forming the low transmission layer in the metal mode andthe reactive gas introduced when forming the high transmission layer inthe poison mode are required to be the same type of gas, while the flowrates and partial pressures of the reactive gases introduced as well asthe pressure inside the vacuum chamber may not be the same.

In the method for manufacturing a mask blank according to theaforementioned second embodiment, a configuration is preferably employedin which the material of the aforementioned target is silicon. Namely,the aforementioned target is preferably a silicon target. According tothe present configuration, the resulting phase-shift film having alaminated structure is composed of a reaction product of silicon and thereactive gas and does not comprise a transition metal and the like. Aphase-shift portion obtained from a phase-shift film deposited in such aconfiguration is resistant to changes in pattern dimensions even ifirradiated for a long period of time with exposure light of a shortwavelength, and more specifically, exposure light of an ArF excimerlaser having a wavelength of 193 nm.

In the method for manufacturing a mask blank according to theaforementioned second embodiment, the aforementioned reactive gas ispreferably nitrogen gas. “Nitrogen gas” as referred to here refers to agas that enables a layer substantially in the form of a nitride to beformed by reactive sputtering. More specifically, the “nitrogen gas”referred to here is preferably a gas in which the content of nitrogen(N₂) that comprises the reactive gas is not less than 90 vol %, andpreferably not less than 99 vol %.

An oxide, nitride or oxynitride and the like is selected in the case offorming a phase-shift film having optical semi-transparency with respectto exposure light of an ArF excimer laser. Although an oxide, nitride oroxynitride and the like is also selected in the case of a silicon-basedphase-shift film, refractive index (n) tends to become low when an oxideor oxynitride is selected. Consequently, in the case oxygen comprisesthe composition of a silicon-based phase-shift film, it becomesnecessary to increase thickness when forming the phase-shift film. Inaddition, in the case of having deposited a silicon-based phase-shiftfilm comprised of oxygen on a transparent substrate composed ofsynthetic quartz glass, there is the problem of it being difficult toobtain etching selectivity between the silicon-based phase-shift filmand the substrate during dry etching carried out when forming a maskpattern. According to the present configuration, a mask blank can bemanufactured that is provided with a phase-shift film that has superioroptical characteristics as well as superior etching selectivity with atransparent substrate composed of quartz glass.

In the method for manufacturing a mask blank according to theaforementioned second embodiment, the aforementioned low transmissionlayer is preferably deposited in a layer having the refractive index (n)with respect to exposure light of an ArF excimer laser of less than 2.4and the extinction coefficient (k) of not less than 1.0, while the hightransmission layer is preferably formed (deposited) in a layer havingthe refractive index (n) with respect to exposure light of an ArFexcimer laser of not less than 2.4 and the extinction coefficient (k)with respect to exposure light of an ArF excimer laser of less than 1.0.A phase-shift film having desired optical characteristics can bedeposited by laminating layers in which the refractive index (n) andextinction coefficient (k) of the low transmission layer and hightransmission layer are adjusted to within the aforementioned ranges.

The refractive index (n) of the low transmission layer is preferably notmore than 2.3, more preferably not more than 2.2 and even morepreferably not more than 2.0. The extinction coefficient (k) of the lowtransmission layer is preferably not less than 1.1, more preferably notless than 1.4 and even more preferably not less than 1.6. In addition,the refractive index (n) of the high transmission layer is preferablynot less than 2.5. The extinction coefficient (k) of the hightransmission layer is preferably not more than 0.9, more preferably notmore than 0.7 and even more preferably not more than 0.4. Furthermore,the refractive index (n) and extinction coefficient (k) of a thin filmare not determined by the composition of the thin film alone, but rathervary according to the film density and crystalline state thereof.Consequently, a thin film is preferably deposited by adjusting thevarious conditions when depositing the thin film by reactive sputteringso that the thin film has a desired refractive index (n) and extinctioncoefficient (k).

In the method for manufacturing a mask blank according to theaforementioned second embodiment, the aforementioned laminated structurein which the low transmission layer and high transmission layer arelaminated in any order is preferably a structure in which three or morelayers of the low transmission layer and high transmission layer arealternately laminated. Even if the elements that compose each layer ofthe low transmission layer and high transmission layer are the same, thecomposition ratios thereof are different from each other. Even if filmsare deposited with the same elements, if the composition ratios aredifferent from each other, the etching rates during dry etching aredifferent from each other. For example, in the case of forming a patternby dry etching with a fluorine-based gas, a level difference occurs inthe wall surfaces of the pattern when layers having different etchingrates are laminated. Reducing the thickness of the laminated layers iseffective for inhibiting this phenomenon. According to the presentconfiguration, since the film thickness of layers composing aphase-shift film can be decreased (to, for example, not more than 20nm), the aforementioned level difference attributable to differences inthe etching rate or each layer can be reduced.

In the method for manufacturing a mask blank according to theaforementioned second embodiment, an oxidized layer is preferably formedon the surface of a phase-shift film having a laminated structure inwhich the aforementioned low transmission layer and the aforementionedhigh transmission layer are laminated in any order. The formation of anoxidized layer as referred to here refers to, for example, aconfiguration in which an oxidized layer is formed by carrying outoxidation treatment after having deposited the phase-shift film having alaminated structure, in which the low transmission layer and the hightransmission layer are laminated in any order by sputtering, and aconfiguration in which a thin film of silicon oxide, for example, isseparately formed on the surface of the phase-shift film having alaminated structure in which the low transmission layer and the hightransmission layer are laminated in any order. Examples of methods usedto carry out oxidation treatment on the surface include a method inwhich the surface of the phase-shift film is heated in air or an oxygenatmosphere, and a method in which ozone or oxygen plasma is contactedwith the surface of the phase-shift film. An example of a method used toseparately form an oxidized layer on the surface of the aforementionedphase-shift film having a laminated structure is sputtering depositionusing silicon dioxide for the target.

In a substrate on which the surface of a thin film that has not beenoxidized is exposed, the surface layer is easily oxidized by cleaningand storing in air. In the case of a phase-shift film, opticalcharacteristics of the thin film during deposition end up changinggreatly due to oxidization of the surface. In the case of aconfiguration in which the low transmission layer is provided for theuppermost layer of a phase-shift film in particular, the amount of theincrease in transmittance caused by oxidization of the low transmissionlayer is thought to become large. Oxidization of the surface of the lowtransmission layer and high transmission layer can be inhibited byforming an oxide layer, which does not have an effect on opticalcharacteristics of the phase-shift film, on (the surface of) a laminatedstructure of the low transmission layer and high transmission layer(laminated in any order).

The following provides a list of preferred modes of the method formanufacturing a mask blank and the method for manufacturing aphase-shift mask described in examples according to the aforementionedsecond embodiment.

(Mode 1)

The mask blank is provided with a phase-shift film having a functionthat causes a predetermined amount of phase shift to be generated withrespect to exposure light of an ArF excimer laser. In addition, thetransparent substrate is a synthetic quartz glass substrate.

(Mode 2)

The layer of the phase-shift film that contacts the transparentsubstrate is a silicon nitride layer (low transmission layer) sputteredin the metal mode. Although the synthetic quartz glass substrate isdry-etched with the same etching gas as that of the silicon nitridelayer, since the silicon nitride layer deposited in the metal mode andhaving a low silicon content has different etching characteristics fromthose of synthetic quartz glass, it has excellent etching selectivity.

(Mode 3)

The layer of the phase-shift film that contacts the transparentsubstrate is a high transmission layer composed of silicon nitridesputtered in the poison mode. In the case of forming a nitride film oroxide film on a synthetic quartz substrate by reactive sputtering, afilm having a high degree of nitridization or high degree of oxidationhas the characteristic of superior adhesion. Adhesion between thephase-shift film and transparent substrate improves as a result of usinga silicon nitride layer (high transmission layer), having a high degreeof nitridization and deposited in the poison mode, for the layer thatcontacts the substrate.

(Mode 4)

Silicon nitride films having different degrees of nitridization for eachtarget are formed for the low transmission layer and high transmissionlayer. The degree of nitridization of the silicon nitride layer (hightransmission layer) is relatively larger than the degree ofnitridization of the silicon nitride layer (low transmission layer). Thedegree of nitridization of (high transmission layer) silicon nitridelayer includes the case in which the nitrogen content is greater than 50at % and the remainder is silicon. The degree of nitridization of thesilicon nitride (low transmission layer) layer includes the case inwhich the nitrogen content is less than 50 at % and the remainder issilicon.

(Mode 5)

The sputtering apparatus used when forming the phase-shift film is an RFsputtering apparatus. In the case of DC sputtering, although varyingaccording to the type of target, when reactive sputtering is carried outin the poison mode, electrical conductivity of the target surfaceportion becomes poor and it becomes difficult to apply a voltage.Consequently, discharge becomes unstable and the high transmission layeris not formed stably. In addition, ion beam sputtering has the problemof a slow deposition rate. According to RF sputtering, the phase-shiftfilm can be deposited stably at a comparatively rapid deposition rateeven in the case of a silicon target in which there is a significantdecrease in electrical conductivity of the target surface in the case ofdepositing in the poison mode.

(Mode 6)

The conditions of the sputtering gas when depositing in the metal modeand poison mode are such that flow rate ratio and other depositionconditions are selected that enable stable deposition in both the metalmode and poison mode by preliminarily verifying the relationship betweendeposition rate and the flow rate ratio between the inert gas andreactive gas in the sputtering gas with the single-wafer RF sputteringapparatus used.

(Mode 7)

Transmittance of the phase-shift film of the phase-shift mask blank withrespect to exposure light of an ArF excimer laser is adjusted to bewithin the range of 1% to 30%. In addition, in the phase-shift film, thephase difference generated between exposure light of an ArF excimerlaser that has transmitted through the phase-shift film and light thathas transmitted through air over the same distance as the thickness ofthe phase-shift film is adjusted to be within the range of 170 degreesto 190 degrees. A phase-shift mask having superior transfer precisioncan be manufactured by manufacturing a mask blank in which transmittanceand phase difference of the phase-shift film have been adjusted so as tobe within the aforementioned ranges.

(Mode 8)

The phase-shift film has two or more sets of a laminated structureconsisting of a low transmission layer and a high transmission layer.The thickness of each layer is not more than 30 nm. As was previouslydescribed, the composition ratios of elements composing the lowtransmission layer and high transmission layer are different from eachother and the difference in etching rates during dry etching is large.Consequently, when a mask pattern is formed by carrying out isotropicdry etching with a fluorine-based gas and the like, a level differenceis formed in the pattern sidewalls. As a result of limiting thethickness of each layer of the low transmission layer and hightransmission layer to not more than 30 nm, and preferably not more than20 nm, level differences occurring in the sidewalls of the pattern ofthe phase-shift film after etching can be more effectively inhibited.

(Mode 9)

A light shielding film is formed on the phase-shift film duringmanufacturing of a mask blank. In a transfer mask, an optical density(OD) of a predetermined value or higher is required to be secured forthe outer peripheral region of the region where the transfer pattern isformed (transfer pattern formation region). This is to prevent theresist film from being affected by exposure light that has transmittedthrough the outer peripheral region when exposing and transferring tothe resist film on a semiconductor wafer using an exposure apparatus.This applies similarly to the case of a phase-shift mask. Normally, inthe outer peripheral region of a transfer mask comprising a phase-shiftmask, the OD thereof is preferably not less than 3.0 and required to benot less than at least 2.8. As was previously described, the phase-shiftfilm has a function to transmit exposure light therethrough at apredetermined transmittance, and it is difficult to secure opticaldensity of a predetermined value with a phase-shift film alone.Consequently, a light shielding film is preferably laminated on thephase-shift film at the stage of manufacturing the mask blank in orderto compensate for the deficient optical density. As a result ofemploying this configuration for the mask blank, a phase-shift mask canbe manufactured that secures a predetermined value of optical densityfor the outer peripheral region if the light shielding film of a regionthat uses phase-shift effects (basically the transfer pattern formationregion) is removed at an intermediate point in the manufacturing of thephase-shift film. Furthermore, a single layer structure or a laminatedstructure having two or more layers can be applied for the lightshielding film.

(Mode 10)

The light shielding film is formed from a material containing chromiumthat has selectivity with respect to the etching gas used when forming apattern in the phase-shift film. Examples of materials containingchromium that form this light shielding film include, in addition tochromium metal, materials containing chromium and one or more elementsselected from oxygen, nitrogen, carbon, boron and fluorine. In general,although chromium-based materials are etched with a mixed gas of achlorine-based gas and oxygen gas, the etching rate of chromium metalwith respect to this etching gas is not very high. When consideringenhancing the etching rate with respect to a mixed gas of achlorine-based gas and oxygen gas, a material containing chromium andone or more elements selected from oxygen, nitrogen, carbon, boron andfluorine is preferable for the material that forms the light shieldingfilm. In addition, the material containing chromium that forms the lightshielding film may also contain one or more elements selected from tin,indium and molybdenum.

(Mode 11)

In the manufacturing of a mask blank, an etching mask is formed on thelight shielding film. Here, an “etching mask” refers to a thin filmformed from a material having etching selectivity with respect to theetching gas used when etching the light shielding film. Since the lightshielding film is required to have a function that secures apredetermined optical density, there are limitations on the degree towhich the thickness thereof can be reduced. The etching mask film isonly required to have a film thickness that enables it to function as anetching mask until completion of dry etching for forming a pattern inthe light shielding film directly there below, and is basically notsubject to any restrictions on optical characteristics. Consequently,the thickness of the etching mask film can be greatly reduced incomparison with the thickness of the light shielding film. Since aresist film of an organic material to be subsequently described is onlyrequired to have a film thickness that allows it to function as anetching mask until completion of dry etching for forming a pattern inthis etching mask film, the thickness of the resist film can also begreatly reduced in comparison with the prior art.

An example of the material of the etching mask in the case of formingthe light shielding film with a material containing chromium is asilicon-based material. An explanation of the silicon-based materialwill be subsequently provided. Furthermore, in the case the lightshielding film is formed from a material containing chromium, a materialcontaining tantalum can also be applied. Examples of materialscontaining tantalum in this case include tantalum metal and materialscontaining tantalum and one or more elements selected from nitrogen,oxygen, boron, silicon and carbon. Examples thereof include Ta, TaN,TaON, TaBN, TaBON, TaCN, TaCON, TaBCN, TaBOCN, TaSi, TaSiN and TaSiON.In addition, in the case the light shielding film is formed from amaterial containing silicon, the etching mask film is preferably formedfrom a material containing chromium. Furthermore, other matters relatingto the light shielding film (including matters relating to a laminatedstructure with the phase-shift film) are the same as those of the lightshielding film according to the previously described first embodiment.

(Mode 12)

Other matters relating to the etching mask film are the same as those ofthe etching mask film according to the previously described firstembodiment.

(Mode 13)

A resist film of an organic material is formed on the surface of theaforementioned etching mask. Other matters relating to the resist filmare the same as those of the resist film according to the previouslydescribed first embodiment.

Third Embodiment

The following provides an explanation of a third embodiment of thepresent disclosure.

During typical manufacturing of a mask blank, a thin film in the mannerof a phase-shift film is deposited on a main surface of a transparentsubstrate by a single-wafer sputtering apparatus. In a mask blank andphase-shift mask having a phase-shift film on a transparent substrate inparticular, it is important that uniformity of the transmittance andamount of phase shift of the phase-shift film is maintained within theplane of the transparent substrate. Consequently, as disclosed in JP2002-90978A, in the deposition of a phase-shift film on a main surfaceof a transparent substrate, deposition is carried out by applyingoblique incidence rotary sputtering in which the sputtered surface of asputtering target is inclined and arranged in opposition to a mainsurface of a rotated transparent substrate.

However, when manufacturing the aforementioned mask blank, even ifmicroscopic scratches (defects) are present on a main surface of thetransparent substrate, if the position of a defective portionsignificantly impairs formation of a transfer pattern, there are casesin which the transparent substrate may be judged to be usable and a maskblank may be fabricated by depositing a thin film. This is because, ifinformation relating to the planar coordinates and type of defect(convex defect or concave defect) in the transparent substrate aretransferred attached to a corresponding mask blank, the thin film can beadjusted to a position where the defective portion does not have aneffect on exposure and transfer when forming a transfer pattern on thethin film.

However, in the deposition of a phase-shift film by applying thepreviously described oblique incidence rotary sputtering, if amicroscopic concave defect is present on a main surface of thetransparent substrate, a low-density region having a lower density thanthe surrounding portions of the transparent substrate was determined tobe partially formed in a phase-shift film deposited on this concavedefect. This is presumed to be due to the occurrence of variations inthe approach angle and speed of particles arriving at the transparentsubstrate during deposition by oblique incidence rotary sputtering sincesputter particles that have been scattered from the sputtering targetapproach from a direction at an angle from the direction perpendicularto a main surface of the transparent substrate and the shape of thecross-section of the concave defect is frequently rounded.

This type of low-density region becomes a region that has highertransmittance and different optical characteristics from surroundingregions. In the case of manufacturing a phase-shift mask from such amask blank in which concave defects are present on a transparentsubstrate, it appears at a glance that a pattern can be designed inwhich concave defects do not have an effect on exposure and transfer ofa fine pattern by covering the concave defects with a phase-shift filmhaving a large area that does not utilize the aforementioned phasedifference. However, since it is difficult to lower transmittance at theportion of a concave defect to the same degree as transmittance at thesurrounding portion where the transfer pattern is present, in the caseof carrying out pattern exposure and transfer on a transfer target (suchas a resist film on a semiconductor substrate) using the completedphase-shift mask, there are cases in which defective transfer occurs inwhich that portion ends up being exposed to the transfer target due tothe high transmittance of the phase-shift film on the concave defect,thereby resulting in a problem.

In this third embodiment, an aspect is to provide a mask blank andphase-shift mask that do not have clear defects where transmittance ishigher than surrounding portions even in the case a transparentsubstrate has microscopic concave defects, and are able to reduce theoccurrence of defective transfer as a result thereof, a method formanufacturing this mask blank, a method for manufacturing a phase-shiftmask, and a method for manufacturing a semiconductor device.

This third embodiment has the configurations indicated below as meansfor solving the aforementioned problems.

(Configuration 1B)

A mask blank provided with a phase-shift film on a main surface of atransparent substrate, wherein

the transparent substrate has a concave defect on the main surface onthe side where the phase-shift film is formed,

the phase-shift film comprises a structure in which a high transmissionlayer and a low transmission layer, having lower optical transmittancethan the high transmission layer, are laminated in that order from theside of the transparent substrate,

an internal region of the high transmission layer of the portion formedon the concave defect has a low-density region, and

the density in the low-density region is relatively lower than thedensity in the internal region of the high transmission layer of aportion formed on the main surface where the concave defect is absent.

(Configuration 2B)

The mask blank of Configuration 1B, wherein the high transmission layerand the low transmission layer are formed from a material containingsilicon and nitrogen, and the high transmission layer has a relativelyhigher nitrogen content in comparison with the low transmission layer.

(Configuration 3B)

The mask blank described in Configuration 1B or Configuration 2B,wherein the high transmission layer and the low transmission layer areformed from a material consisting of silicon and nitrogen or a materialconsisting of silicon, nitrogen and one or more elements selected fromsemi-metallic elements, non-metallic elements and noble gases.

(Configuration 4B)

The mask blank described in any of Configurations 1B to 3B, wherein thehigh transmission layer and the low transmission layer are composed ofthe same constituent elements.

(Configuration 5B)

The mask blank described in any of Configurations 1B to 4B, wherein thephase-shift film has two or more sets of combinations of a laminatedstructure consisting of the low transmission layer and the hightransmission layer.

(Configuration 6B)

The mask blank described in any of Configurations 1B to 5B, wherein thehigh transmission layer and the low transmission layer are formed from amaterial consisting of silicon and nitrogen.

(Configuration 7B)

The mask blank described in any of Configurations 1B to 6B, wherein thehigh transmission layer has a larger film thickness than the lowtransmission layer.

(Configuration 8B)

The mask blank described in any of Configurations 1B to 7B, wherein thephase-shift film is provided with an uppermost layer formed from amaterial containing silicon and oxygen at a position farthest away fromthe transparent substrate.

(Configuration 9B)

The mask blank described in any of Configurations 1B to 8B, wherein thephase-shift film is provided with an uppermost layer at a positionfarthest away from the transparent substrate, and the uppermost layerformed from a material consisting of silicon and oxygen, a materialconsisting of silicon, nitrogen and oxygen, or a material containing oneor more elements selected from semi-metallic elements, non-metallicelements and noble gases in those materials.

(Configuration 10B)

The mask blank described in Configuration 8B or Configuration 9B,wherein the phase-shift film formed on the concave defect remains evenafter carrying out hot water cleaning for not less than 5 minutes on thephase-shift film.

(Configuration 11B)

A phase-shift mask comprising a transfer pattern formed on thephase-shift film of the mask blank described in any of Configurations 1Bto 10B.

(Configuration 12B)

A method for manufacturing a mask blank provided with a phase-shift filmon a main surface of a transparent substrate, provided with:

a step of depositing the phase-shift film on a main surface of thetransparent substrate having a concave defect by a sputtering methodthat comprises rotating the transparent substrate about an axis ofrotation that passes through the center of the main surface andarranging the sputtered surface of the sputtering target at an angle inopposition to the main surface of the transparent substrate having aconcave defect; wherein,

the step of forming the phase-shift film comprises a high transmissionlayer formation step of forming a high transmission layer on the mainsurface of the transparent substrate having a concave defect, and a lowtransmission layer formation step of forming a low transmission layer,having optical transmittance that is lower than that of the hightransmission layer, on the high transmission layer, and

in the high transmission layer formed in the high transmission layerformation step, an internal region of the portion of the hightransmission layer formed on the concave defect has a low-densityregion, and the density in the low-density region is relatively lowerthan the density in the internal region of the portion of the hightransmission layer formed on a main surface where the concave defect isabsent.

(Configuration 13B)

The method for manufacturing a mask blank described in Configuration12B, wherein the high transmission layer formation step forms the hightransmission layer by reactive sputtering in a sputtering gas thatcomprises a nitrogen-based gas and a noble gas using the sputteringtarget composed of a material containing silicon, and

the low transmission layer formation step forms the low transmissionlayer by reactive sputtering in a sputtering gas that comprises anitrogen-based gas and a noble gas, in which the mixing ratio ofnitrogen-based gas is lower than during the high transmission layerformation step, using the sputtering target composed of a materialcontaining silicon.

(Configuration 14B)

The method for manufacturing a mask blank described in Configuration 12Bor Configuration 13B, wherein the high transmission layer formation stepforms the high transmission layer by reactive sputtering in a sputteringgas that comprises a nitrogen-based gas and a noble gas using thesputtering target composed of material containing silicon or containingone or more elements selected from semi-metallic elements andnon-metallic elements in silicon, and

the low transmission layer formation step forms the low transmissionlayer by reactive sputtering in a sputtering gas that comprises anitrogen-based gas and a noble gas, in which the mixing ratio ofnitrogen-based gas is lower than during the high transmission layerformation step, using the sputtering target composed of materialcontaining silicon or containing one or more elements selected fromsemi-metallic elements and non-metallic elements in silicon.

(Configuration 15B)

The method for manufacturing a mask blank described in any ofConfigurations 12B to 14B, wherein the high transmission layer formationstep forms the high transmission layer by reactive sputtering in asputtering gas composed of nitrogen gas and a noble gas using thesputtering target composed of silicon, and

the low transmission layer formation step forms the low transmissionlayer by reactive sputtering in a sputtering gas composed of nitrogengas and a noble gas, and in which the mixing ratio of nitrogen-based gasis lower than during the high transmission layer formation step, usingthe sputtering target composed of silicon.

(Configuration 16B)

The method for manufacturing a mask blank described in any ofConfigurations 12B to 15B, wherein the high transmission layer formationstep forms the high transmission layer by reactive sputtering in apoison mode, and

the low transmission layer formation step forms the low transmissionlayer by reactive sputtering in a metal mode.

(Configuration 17B)

The method for manufacturing a mask blank described in any ofConfigurations 12B to 16B, having an uppermost layer formation step offorming an uppermost layer composed of a material containing silicon andoxygen at a position of the phase-shift film farthest away from thetransparent substrate.

(Configuration 18B)

The method for manufacturing a mask blank described in any ofConfigurations 12B to 17B, having an uppermost layer formation step offorming an uppermost layer with a material composed of silicon andoxygen, a material composed of silicon, nitrogen and oxygen, or amaterial containing one or more elements selected from semi-metallicelements, non-metallic elements and noble gases in those materials, at aposition of the phase-shift film farthest away from the transparentsubstrate.

(Configuration 19B)

A method for manufacturing a phase-shift mask having a step of forming atransfer pattern on the phase-shift film of the mask blank manufacturedaccording to the method for manufacturing a mask blank described in anyof Configurations 12B to 18B.

(Configuration 20B)

A method for manufacturing a semiconductor device, provided with a stepof exposing and transferring the transfer pattern of the phase-shiftmask to a resist film on a substrate using the phase-shift maskdescribed in Configuration 11B.

(Configuration 21B)

A method for manufacturing a semiconductor device, provided with a stepof exposing and transferring the transfer pattern of the phase-shiftmask to a resist film on a substrate using a phase-shift maskmanufactured according to the method for manufacturing a phase-shiftmask described in Configuration 19B.

According to each configuration of the aforementioned third embodiment,as a result of adopting a configuration in which a low-density region isformed on a concave defect in a high transmission layer provided on theside of a transparent substrate, transmittance of a phase-shift film canmainly be controlled by a low transmission layer not comprising alow-density region. Consequently, in-plane uniformity of transmittanceof the phase-shift film on the transparent substrate having a concavedefect can be improved, and as a result thereof, the formation of cleardefects in a mask blank and phase-shift mask can be inhibited, therebymaking it possible to prevent the occurrence of defective transfer usingthe phase-shift mask.

In the manufacturing of a mask blank, when depositing a thin film on amain surface of a transparent substrate, film deposition is carried outby applying oblique incidence rotary sputtering in which the sputteredsurface of a sputtering target is inclined and arranged in opposition toa main surface of a rotated transparent substrate.

However, in a mask blank obtained by depositing a thin film of atransition metal silicide-based material represented by an MoSi-basedmaterial by applying this type of oblique incidence rotary sputtering,there have been determined to be cases in which microscopic pinholedefects (measuring about 100 nm) are formed in a main surface of thethin film during the process for fabricating a transfer mask using thismask blank. In addition, even though defects are not detected in a maskdefect inspection carried out immediately after fabricating the transfermask, when a mask defect inspection is carried out after mask cleaningthat is carried out after using for a predetermined number of times withplacing the transfer mask in an exposure apparatus, microscopic pinholedefects were determined to be similarly formed on a main surface of thethin film. In either of these cases, such pinhole defects were notdetected when a defect inspection was carried out on a mask blankobtained by depositing a thin film.

The inventors of the present disclosure conducted extensive research onthe cause of this formation of pinhole defects. As a result, scratches(concave defects) of a microscopic depth (not more than 40 nm) weredetermined to be present on a main surface of the transparent substratedirectly below the pinhole defect in all of the mask blanks in whichpinhole defects had formed as previously described. Next, transmissionelectron micrographs (TEM) of concave defects were observed in a maskblank manufactured with a transparent substrate in which microscopicconcave defects are present. As a result, uneven deposition was able tobe confirmed to have occurred in a thin film on the concave defects.

As a result of conducting additional research on this portion of unevendeposition, this portion of uneven deposition was determined to have alower density in comparison with other portions of the thin film.Moreover, the region of low density where this uneven depositionoccurred (low-density region) exhibited a shape in which it extendedfrom the side of the transparent substrate towards the surface side ofthe thin film in a cross-sectional view thereof, and was able to beconfirmed to be extending from near the outer periphery of the concavedefects towards the center in an overhead view thereof.

The cause of the formation of this low-density region as described aboveis presumed to be due to the occurrence of variations in the approachangle and speed of particles arriving at the transparent substrateduring deposition of the thin film by oblique incidence rotarysputtering since sputter particles that have been scattered from thesputtering target approach from a direction at an angle from thedirection perpendicular to a main surface of the transparent substrateand the shape of the cross-section of the concave defect is frequentlyrounded.

The problem here is that a low-density region in a thin film asdescribed above is a region of high transmittance in comparison withsurrounding portions of the thin film. Consequently, even if a thin filmon a transparent substrate is composed with a material for which thereis no concern over the formation of pinhole defects, for example, ifthis thin film is a phase-shift film, it is difficult to holdtransmittance at a concave defect to a low level similar to thetransmittance of the surrounding portions of the thin film whilemaintaining a predetermined amount of phase shift. Thus, even if apattern is designed for a phase-shift mask in which concave defects arepresent in a transparent substrate that covers the concave defects witha phase-shift film having a large area that does not utilize a phasedifference, it is difficult to hold the transmittance at a concavedefect to a low level similar to the transmittance of surroundingportions where a transfer pattern is present, thereby resulting in therisk of the occurrence of clear defects.

Therefore, in each mask blank according to the third embodiment, aphase-shift film on a main surface of a transparent substrate has aconfiguration in which a high transmission layer and a low transmissionlayer are laminated from the side of the transparent substrate. Sincethe high transmission layer is inherently a layer that has hightransmittance, even if a low-density region is partially formed in thishigh transmission layer, the degree of increase in transmittancethroughout the entire phase-shift film in the direction of filmthickness attributable thereto is low, and even if a phase-shift mask isfabricated using a mask blank having such a phase-shift film, the effectof the low-density region on pattern exposure and transfer can be heldto a low level.

In addition, when fabricating a phase-shift mask from a mask blank, apattern is typically arranged so that the phase-shift film on a concavedefect of the transparent substrate does not become a region that formsa fine transfer pattern. Consequently, there are substantially noproblems with respect to the amount of phase shift of the phase-shiftfilm on the concave defect even if it is not within a predeterminedrange. Thus, even if a low-density region is partially formed in thehigh transmission layer mainly used to adjust the amount of phase shiftof the phase-shift film, this does not present a problem whenfabricating a phase-shift mask.

The following provides an explanation of detailed configurations of thepresent disclosure as previously described, based on the drawings.Furthermore, the same reference symbols are used to explain the sameconstituent members in each of the drawings.

<<Mask Blank>>

FIG. 7 is a cross-sectional view of the essential portions of a maskblank 300 indicating one example of the configuration of the thirdembodiment. As shown in the drawing, the mask blank 300 has aconfiguration in which a halftone phase-shift film (to be referred to asa phase-shift film) 320 is provided on a main surface S on one side of atransparent substrate 301. The phase-shift film 320 has a laminatedstructure 324, in which a high transmission layer 322 and a lowtransmission layer 321, having lower transmittance than the hightransmission layer 322, are laminated in that order from the side of thetransparent substrate 301. In addition, the phase-shift film 320 mayalso be provided with an uppermost layer 323 at a position farthest fromthe transparent substrate 301. In this type of phase-shift film 320,each layer is deposited by oblique incidence rotary sputtering to besubsequently described in detail. In addition, the mask blank 300 mayalso employ a configuration in which a light shielding film 303, anetching mask film 304 and a resist film 305 are laminated in that orderas necessary on the upper portion of the phase-shift film 320. Thefollowing provides a detailed explanation of essential constituentmembers of the mask blank 300.

<Transparent Substrate 301>

The transparent substrate 301 has a scratch of a microscopic depth inthe form of a concave defect F on the main surface S on the sideprovided with the phase-shift film 320. The depth of the concave defectF is, for example, not more than 40 nm.

This type of transparent substrate 301 is composed of a material havingfavorable transparency with respect to exposure light used in alithography exposure step. In the case of using ArF excimer laser light(wavelength: about 193 nm) for the exposure light, the transparentsubstrate 301 is composed with a material having favorable transparencywith respect thereto. Although synthetic quartz glass is used for such amaterial, aluminosilicate glass, soda lime glass, low thermal expansionglass (such as SiO₂—TiO₂ glass) or various other types of glasssubstrates can also be used. Since quartz substrates in particular havehigh transparency with respect to ArF excimer laser light or light of aregion having a shorter wavelength than that light, it can be usedpreferably in the mask blank of the aforementioned third embodiment.

Furthermore, the lithography exposure step here refers to a lithographyexposure step using a phase-shift mask fabricated using this mask blank1, and exposure light hereinafter refers to the exposure light used inthis exposure step. Although ArF excimer laser light (wavelength: 193nm), KrF excimer laser light (wavelength: 248 nm) or i-line light(wavelength: 365 nm) can be applied for this exposure light, from theviewpoint of miniaturization of a transfer pattern in the exposure step,ArF excimer laser light is preferably applied for the exposure light.Consequently, the following embodiments are explained for the case ofusing ArF excimer laser light for the exposure light.

<High Transmission Layer 322, Low Transmission Layer 321>

Among the high transmission layer 322 and the low transmission layer 321composing the phase-shift film 320, the high transmission layer 322provided on the side of the transparent substrate 301 is a layer that ismainly used to adjust the amount of phase shift in the phase-shift film320. In this high transmission layer 322, an internal region of aportion formed on the concave defect F of the transparent substrate 301has a low-density region D. The low-density region D in the hightransmission layer 322 has a relatively lower density than the densityin an internal region of the portion of the high transmission layer 322formed on the main surface S where there is no concave defect F in thetransparent substrate 301.

In addition, the low transmission layer 321 is a layer provided on theside of the main surface S of the transparent substrate 301 with thehigh transmission layer 322 interposed there between, and thetransmittance thereof is lower than that of the high transmission layer322. This type of low transmission layer 321 is a layer that is mainlyused to adjust transmittance in the phase-shift film 320. In addition,the low-density region D formed on the concave defect F does not reachthis low transmission layer 321.

The high transmission layer 322 and the low transmission layer 321 asdescribed above are formed from a material containing silicon andnitrogen, and the nitrogen content of the high transmission layer 322 isrelatively high in comparison with the low transmission layer 321. Thehigh transmission layer 322 and the low transmission layer 321 may beformed with (1) a material consisting of silicon and nitrogen or (2) amaterial containing one or more elements selected from semi-metallicelements, non-metallic elements and noble gases in the material (1).

Although a semi-metallic element contained in the high transmissionlayer 322 and the low transmission layer 321 may be, in addition tosilicon, any semi-metallic element, it is particularly one or moreelements selected from boron, germanium, antimony and tellurium. Theseelements are elements that are contained in the high transmission layer322 and the low transmission layer 321 due to the deposition process ofthe phase-shift film 320 carried out by sputtering to be subsequentlyexplained, and are elements that are introduced in order to enhanceelectrical conductivity of a sputtering target that uses silicon.

A non-metallic element contained in the high transmission layer 322 andthe low transmission layer 321 may be, in addition to nitrogen, anynon-metallic element. Among these, one or more elements selected fromcarbon, fluorine and hydrogen is preferably contained in the hightransmission layer 322 and the low transmission layer 321. On the otherhand, the oxygen content of the high transmission layer 322 and the lowtransmission layer 321 is preferably held to not more than 10 at %, theoxygen content is preferably not more than 5 at %, and even morepreferably, not containing oxygen actively (such that the result of RBS,XPS or other composition analyses is below the detection limit). In thismanner, as a result of reducing oxygen content to a low level insilicon-based material films in the form of the high transmission layer322 and the low transmission layer 321, the value of extinctioncoefficient k can be maintained to a certain degree and the overallthickness of the phase-shift film 320 can be reduced.

In addition, in the case the transparent substrate 301 is formed from amaterial having a synthetic quartz glass such as SiO₂ as the maincomponent thereof, as a result of holding the oxygen content in the hightransmission layer 322 provided in contact with the transparentsubstrate 301 to a low level, a composition difference can be securedbetween the transparent substrate 301 and the high transmission layer322. As a result, etching selectivity between the phase-shift film 320and the transparent substrate 301 can be made to be large during etchingwhen forming a phase-shift mask by patterning the phase-shift film 320.

A noble gas contained in the high transmission layer 322 and the lowtransmission layer 321 is an element that is contained in the hightransmission layer 322 and the low transmission layer 321 due to thedeposition process of the phase-shift film 320 carried out by sputteringto be subsequently explained. The noble gas is an element that makes itpossible to increase deposition rate and improve productivity as aresult of being present in the deposition chamber when depositing thephase-shift film 320 by reactive sputtering. During film deposition byreactive sputtering, as a result of this noble gas being plasmified andcolliding with a target, constituent elements of the target arescattered from the target and a thin film is formed by being laminatedon a transparent substrate while incorporating reactive gas at anintermediated point. A small amount of noble gas in the depositionchamber is incorporated during the time until the target constituentelements are scattered from the target and adhere to the transparentsubstrate. Preferable examples of noble gases required by this reactivesputtering include argon, krypton and xenon. In addition, helium and/orneon, having a low atomic weight, can be aggressively incorporated intothe thin film in order to relax stress in the deposited phase-shift film320 comprising the high transmission layer 322 and the low transmissionlayer 321.

The high transmission layer 322 and the low transmission layer 321 asdescribed above preferably employ a structure in which they arelaminated in direct mutual contact without having another filminterposed there between. In addition, the mask blank 300 of the presentdisclosure preferably employs a film structure in which a film composedof a material containing a metal element does not contact either of thehigh transmission layer 322 and the low transmission layer 321. As aresult of employing this configuration, in the case of having carriedout heat treatment or irradiation with ArF exposure light in a state inwhich a film containing a metal element contacts a film containingsilicon, the metal element is not diffused in the film containingsilicon, and changes over time in the compositions of the hightransmission layer 322 and the low transmission layer 321 can be held toa low level.

In addition, the high transmission layer 322 and the low transmissionlayer 321 are preferably composed of the same constituent elements. Inthe case either of the high transmission layer 322 and the lowtransmission layer 321 contain different constituent elements and heattreatment or irradiation with ArF exposure light has been carried out ina state in which they are laminated in contact, there is the risk ofthose different constituent elements migrating to and diffusing into alayer on a side not containing those constituent elements. There is alsothe risk of the optical characteristics of the high transmission layer322 and the low transmission layer 321 ending up changing considerablyfrom those at the time of initial deposition. However, as a result ofthe high transmission layer 322 and the low transmission layer 321 beingcomposed with the same constituent elements, such changes can be held toa low level. In addition, although the high transmission layer 322 andthe low transmission layer 321 must be deposited using different targetsin the case one of the different constituent elements is a semi-metallicelement in particular, this is also not necessary.

In addition, among the high transmission layer 322 and the lowtransmission layer 321, the low transmission layer 321 may contain atransition metal for the purpose of adjusting transmittance of thephase-shift film 320. However, since transition metals can cause lightfastness to ArF exposure light to decrease, a transition metal can becontained in the low transmission layer 321 if this decrease in lightfastness does not present a problem. The low transmission layer 321 mayalso be composed with a material that contains a transition metal butdoes not contain silicon. Examples of transition metals contained in thelow transmission layer 321 include materials containing one or moreelements selected from titanium (Ti), tantalum (Ta), aluminum (Al),zirconium (Zr) and chromium (Cr). The low transmission layer 321containing a transition metal is more preferably any of titanium nitride(TiN), tantalum nitride (TaN), aluminum nitride (AlN), zirconium nitride(ZrN) and chromium nitride (CrN).

In addition, the high transmission layer 322 and the low transmissionlayer 321 are preferably formed from a material consisting of siliconand nitrogen. As a result, a decrease in light fastness attributable tocontaining a transition metal in the high transmission layer 322 and thelow transmission layer 321 can be prevented, and a change in opticalcharacteristics accompanying migration of metal or semi-metallicelements between the high transmission layer 322 and the lowtransmission layer 321, which is attributable to containing a metalother than a transition metal and a semi-metallic element other thansilicon in the high transmission layer 322 and the low transmissionlayer 321, can be prevented. In addition, if a non-metallic element iscontained and oxygen, for example, is contained in the high transmissionlayer 322 and the low transmission layer 321, transmittance with respectto ArF exposure light increases considerably. In consideration thereof,the high transmission layer 322 and the low transmission layer 321 aremore preferably formed from a material consisting of silicon andnitrogen. A noble gas is an element that is difficult to be detectedeven in the case of carrying out a composition analysis such as RBS orXPS on the thin film. Consequently, a material containing a noble gascan be considered to be included in the aforementioned materialconsisting of silicon and nitrogen.

In addition, in the phase-shift film 320 having the high transmissionlayer 322 and the low transmission layer 321 of each of the materials aspreviously described, two or more sets of the laminated structure 324,composed of a single layer of the high transmission layer 322 and asingle layer of the low transmission layer 321, may be laminated whilemaintaining the lamination order of the high transmission layer 322 andthe low transmission layer 321. In this case, the thickness of any onelayer of the high transmission layer 322 and the low transmission layer321 is preferably not more than 20 nm. Since required opticalcharacteristics are greatly different between the high transmissionlayer 322 and the low transmission layer 321, there is a largedifference in film nitrogen content between the two. Consequently, thereis a large difference in etching rates between the high transmissionlayer 322 and the low transmission layer 321 in the case of carrying outdry etching with a fluorine-based gas when patterning these layers. Inthe case the phase-shift film has only one set of the laminatedstructure 324, when forming a transfer pattern on the phase-shift film320 by dry etching with a fluorine-based gas, a level difference easilyoccurs in a cross-section of the pattern of the phase-shift film 320after etching. As a result of the phase-shift film 320 employing astructure that has two or more sets of the laminated structure 324,since the thickness of each layer (one layer) of the high transmissionlayer 322 and the low transmission layer 321 is small in comparison withthe case of having only one set of the laminated structure 324, thelevel difference that occurs in a cross-section of the pattern of thephase-shift film 320 after etching can be made to be small. In addition,as a result of restricting the thickness of each layer (one layer) ofthe high transmission layer 322 and the low transmission layer 321 tonot more than 20 nm, the level difference that occurs in a cross-sectionof the pattern of the phase-shift film 320 after etching can be furtherreduced.

However, the high transmission layer 322 arranged closest to thetransparent substrate 301 preferably has a film thickness that fills inthe concave defect F of the transparent substrate 301 while alsocovering the low-density region D formed on this concave defect F.

Furthermore, as a variation of the mask blank 300, a mask blankconfiguration may be employed in which a phase-shift film, laminated onthe side of the low transmission layer 321 in the laminated structure324 composed of a single layer of the high transmission layer 322 and asingle layer of the low transmission layer 321 and further provided witha single layer of the high transmission layer 322, is provided on thetransparent substrate 301. Similar to that previously explained, two ormore sets of the laminated structure 324 may be laminated, and in thiscase, a configuration results in which a single layer of the hightransmission layer 322 is provided laminated on the low transmissionlayer 321 provided at a position farthest away from the transparentsubstrate 301. As a result, the mask blank has a phase-shift film havinga configuration in which a single layer of the high transmission layer322 is interposed between the laminated structure 324 and the uppermostlayer 323 to be subsequently explained.

In the high transmission layer 322 and the low transmission layer 321 aspreviously described, refractive index n and extinction coefficient kare respectively set to be within a predetermined range so that thephase-shift film 320 composed thereof satisfies a predetermined phasedifference and a predetermined transmittance with respect to an exposurelight (such as ArF excimer laser light).

The high transmission layer 322 is a layer mainly used to adjust theamount of phase shift in the phase-shift film 320. This type of hightransmission layer 322 is preferably formed from a material having, forexample, the refractive index n with respect to ArF excimer laser lightof not less than 2.5 (and preferably not less than 2.6) and theextinction coefficient k of less than 1.0 (and preferably not more than0.9, more preferably not more than 0.7 and even more preferably not morethan 0.4).

In addition, the low transmission layer 321 is a layer mainly used toadjust transmittance of the phase-shift film 320. This type of lowtransmission layer 321 is preferably formed from a material having, forexample, the refractive index n with respect to ArF excimer laser lightof less than 2.5 (and preferably not more than 2.4, more preferably notmore than 2.2 and even more preferably not more than 2.0) and theextinction coefficient k with respect to ArF exposure light of not lessthan 1.0 (and preferably not less than 1.1, more preferably not lessthan 1.4 and even more preferably not less than 1.6).

Here, the refractive index n and extinction coefficient k of a thin filmare not only determined by the composition of that thin film. Factorssuch as the film density or crystalline state of that thin film are alsoelements that have an effect on the refractive index n and extinctioncoefficient k. Consequently, each of these layers is made to have adesired refractive index n and extinction coefficient k by filmdeposition in which various conditions are adjusted when depositing thehigh transmission layer 322 and the low transmission layer 321 thatcompose the phase-shift film 320.

In addition, in the high transmission layer 322 and the low transmissionlayer 321 for which refractive index n and extinction coefficient k havebeen set as described above, the film thickness of the high transmissionlayer 322 is greater than the film thickness of the low transmissionlayer 321. Furthermore, in the case of employing a configuration inwhich a plurality of sets of the laminated structures 324, composed of asingle layer of the high transmission layer 322 and a single layer ofthe low transmission layer 321, are laminated, the total film thicknessof the plurality of high transmission layers 322 is greater than thetotal film thickness of the plurality of low transmission layers 321.Moreover, even in a configuration in which a single layer of the hightransmission layer 322 is laminated for a single or plurality of thelaminated structure 324, the total film thickness of the plurality ofhigh transmission layers 322 is greater than the total film thickness ofthe plurality of the low transmission layers 321.

<Uppermost Layer 323>

The phase-shift film 320 is preferably provided with the uppermost layer323, formed from a material containing silicon and oxygen, at a positionfarthest away from the transparent substrate 301. This uppermost layer323 is formed from (3) a material composed of silicon and oxygen, (4) amaterial composed of silicon, nitrogen and oxygen, or (5) a materialcontaining one or more elements selected from semi-metallic elements,non-metallic elements and noble gases in the material (3) or thematerial (4).

The semi-metallic elements, non-metallic elements and noble gasescontained in the uppermost layer 323 are the same as the semi-metallicelements, non-metallic elements and noble gases contained in the hightransmission layer 322 and the low transmission layer 321.

In addition to including a configuration in which the composition isnearly the same in the direction of layer thickness, the uppermost layer323 composed with these materials also comprises a configuration havinga composition gradient in the direction of layer thickness. Thecomposition gradient in the uppermost layer 323 is such that the layeroxygen content increases moving away from the transparent substrate.Among the uppermost layers 323 having such configurations, examples ofmaterials preferable for a configuration in which the composition isnearly the same in the direction of layer thickness include SiO₂ andSiON. In addition, a preferable example of a configuration having acomposition gradient in the direction of layer thickness is preferably aconfiguration in which SiN is present on the side of the transparentsubstrate 301, the oxygen content increases moving away from thetransparent substrate 301, and the surface layer is SiO₂ or SiON.Furthermore, in this case of this configuration, a layer with acomposition gradient by oxidizing the surface layer of the hightransmission layer 322 or the low transmission layer 321 may also beused for the uppermost layer 323.

As a result of having the phase-shift film 320 having this uppermostlayer 323, chemical resistance is able to be secured for the phase-shiftfilm 320. Namely, the high transmission layer 322 and the lowtransmission layer 321 are formed from a material containing silicon andnitrogen and the oxygen content thereof is held to a low level. In thismanner, although a silicon-based material film containing nitrogen butnot containing oxygen actively demonstrates high light fastness withrespect to ArF excimer laser light, chemical resistance tends to be lowin comparison with a silicon-based material film containing oxygenactively. Thus, as a result of the phase-shift film 320 having theuppermost layer 323 formed from a material containing silicon andoxygen, chemical resistance of the phase-shift film 320 can be improved.

As a result of providing this uppermost layer 323, the phase-shift film320 remains on the concave defect F in this mask blank 300 withoutpinhole defects being formed in the phase-shift film 320 on the concavedefect F even after having carried out hot water cleaning on thephase-shift film 320 for not less than 5 minutes.

In order for the phase-shift film 320, in which each layer is composedin the manner described above (including variations of the phase-shiftfilm and to apply similarly hereinafter), to allow phase-shift effectsto function effectively, transmittance with respect to ArF excimer laserlight is preferably not less than 1% and more preferably not less than2%. In addition, the phase-shift film 320 is preferably adjusted so thattransmittance with respect to ArF excimer laser light is not more than30%, more preferably not more than 20% and even more preferably not morethan 10%. In addition, in the phase-shift film 320, a phase differencegenerated between ArF excimer laser light that transmits therethroughand light that transmits through air over the same distance as thethickness of the phase-shift film 320 is preferably adjusted to bewithin the range of 170 degrees to 190 degrees.

<Light Shielding Film 303>

The mask blank 300 according to the aforementioned third embodiment(including variations of the mask blank, and to apply similarlyhereinafter) preferably has the light shielding film 303 laminated onthe phase-shift film 320. Other matters relating to the light shieldingfilm 303 (including matters relating to a laminated structure with thephase-shift film) are the same as those of the light shielding film 3according to the previously described first embodiment.

<Etching Mask Film 304>

A configuration is more preferably employed in which, in the mask blank300 provided with the light shielding film 303 by laminating on thephase-shift film 320, the etching mask film 304, formed from a materialhaving etching selectivity with respect to the etching gas used whenetching the light shielding film 303, is laminated on the lightshielding film 303. Other matters relating to the etching mask film 304are the same as those of the etching mask film 4 according to theaforementioned first embodiment.

<Resist Film 305>

In the mask blank 300 according to the aforementioned third embodiment,the resist film 305 of an organic material is preferably formed incontact with the surface of the etching mask film 304 at a filmthickness of not more than 100 nm. Other matters relating to the resistfilm 305 are the same as those of the resist film according to theaforementioned first embodiment.

<<Method for Manufacturing Mask Blank>>

The following provides an explanation of the method for manufacturing amask blank according to the aforementioned third embodiment.

<Deposition Apparatus 500>

FIG. 8 shows a schematic diagram of one example of a depositionapparatus 500 used in the method for forming the mask blank 300according to the third embodiment. The deposition apparatus 500 shown inthis drawing is a sputtering deposition apparatus in which filmdeposition is carried out by oblique incidence rotary sputtering. Thisdeposition apparatus 500 is a deposition apparatus that is provided witha rotating stage 531 on which the transparent substrate 301 is placedand a sputtering target 533 arranged in a predetermined state withrespect to this rotating stage 531, and is able to form a thin film bysputtering on the main surface S of the transparent substrate 301. Inthe deposition apparatus 500 able to be used in the manufacturing methodof the present disclosure, the transparent substrate 301 placed on therotating stage 531 and the sputtering target 533 are in a predeterminedpositional relationship.

Namely, the deposition apparatus 500 is characterized in that asputtered surface 533 s of the sputtering target 533 is arranged inopposition to the main surface S of the transparent substrate 301 on therotating stage 531 and above the transparent substrate 301 on an angle.This deposition apparatus 500 is provided with a deposition chamber 535in which the rotating stage 531 and the sputtering target 533 arehoused, and employs a configuration in which a thin film is sputteredand deposited on the transparent substrate 301 within this depositionchamber 535. The deposition chamber 535 has a gas inlet port 537 and anexhaust port 539, and functions as a vacuum chamber that carries outfilm deposition.

FIG. 9 is a schematic diagram showing the positional relationshipbetween the transparent substrate 301 and the sputtering target 533. Asa result of rotating the rotating stage 531, the transparent substrate301 rotates about an axis of rotation ϕ that passes through the centerof the main surface S and is perpendicular to the main surface S.

The sputtering target 533 is arranged so as to have a predeterminedangle of inclination θ (target angle of inclination θ) relative to themain surface S of the transparent substrate 301. In other words, acentral axis ϕ1, which passes through the center O of the sputteringtarget 533 and is perpendicular to the sputtered surface 533 s of thesputtering target 533, is inclined relative to the axis of rotation ϕ ofthe transparent substrate 301.

In addition, the sputtering target 533 is arranged so that the axis ofrotation ϕ of the transparent substrate 301 and a straight line ϕ2,which passes through the center O of the sputtered surface 533 s and isparallel to the axis of rotation ϕ of the transparent substrate 301, arepositioned separated by a predetermined offset distance Doff.

Here, in order to improve in-plane uniformity of the film thickness of athin film deposited on the main surface S of the transparent substrate301, it is necessary that a suitable positional relationship bemaintained between the transparent substrate 301 and the sputteringtarget 533. Consequently, the following provides an additionalexplanation of the positional relationship between the transparentsubstrate 301 and the sputtering target 533 in the deposition apparatus500 of the present disclosure.

As shown in FIGS. 8 and 9, in the deposition apparatus 500 used in thepresent disclosure, the target angle of inclination θ of the sputteredsurface 533 s of the sputtering target 533 with respect to the mainsurface S of the transparent substrate 301 not only has an effect onin-plane uniformity of film thickness in a thin film deposited on themain surface S of the transparent substrate 301, but also has an effecton deposition rate. More specifically, in order to obtain favorablein-plane uniformity of the film thickness of a thin film and in order toobtain a large deposition rate, the target angle of inclination θ issuitably 0 degrees to 45 degrees. In addition, a preferable target angleof inclination θ is 10 degrees to 30 degrees, and as a result thereof,in-plane uniformity of the film thickness of a thin film deposited onthe main surface S of the transparent substrate can be improved.

The offset distance Doff in the deposition apparatus 500 can be adjustedaccording to the area for which in-plane uniformity is to be secured forfilm thickness in a thin film deposited on the main surface S of thetransparent substrate 301. In general, in the case of a large area forwhich favorable in-plane uniformity is to be secured, the requiredoffset distance Doff becomes large. For example, in the case thetransparent substrate 301 with 152 mm on a side, the region where atransfer pattern is formed on a thin film is normally an inside regionwith 132 mm on a side based on the center of the transparent substrate301. In order to realize film thickness distribution of a thin film at aprecision level of within ±1 nm in this inside region with 132 cm on aside, the offset distance Doff is required to be about 240 mm to 400 mm,and the preferable offset distance Doff is 300 mm to 380 mm.

In addition, as a result of providing the offset distance Doff in thismanner, dropping of particles from the sputtered surface 533 s of thesputtering target 533 onto the main surface S of the transparentsubstrate 301 can be prevented during sputtering and deposition. As aresult, particles can be prevented from contaminating the thin filmdeposited on the main surface S of the transparent substrate 301 andcausing defects, thereby making it possible to hold the incidence ofdefects during deposition to a low level.

The optimum range of a vertical distance H between the sputtering target533 and the transparent substrate 301 in the deposition apparatus 500varies according to the offset distance Doff. This vertical distance His the distance from the height position of the transparent substrate301 to the height position of the center O of the sputtering target 533.For example, in order to secure favorable in-plane uniformity in thetransparent substrate 301 with 152 mm on a side, this vertical distanceH is required to be about 200 mm to 380 mm, and the preferable verticaldistance H is 210 mm to 300 mm.

For example, in the case this deposition apparatus 500 is a magnetronsputtering apparatus, the sputtering target 533 is in a state in whichit is attached through a backing plate 543 to a magnetron electrode 541.Furthermore, although deposition of a phase-shift film is carried out byoblique incidence rotary sputtering in the method for manufacturing amask blank according to the aforementioned third embodiment, there areno limitations on the magnetron sputtering apparatus provided obliqueincidence rotary sputtering is applied for the sputtering method, and itmay be an ion beam sputtering apparatus. In addition, in the case ofmagnetron sputtering, the magnetron power supply suitably uses a directcurrent (DC) power supply or radio frequency (RF) power supply dependingon the material of the sputtering target 533. For example, in the caseof using a target 533 having low electrical conductivity (such as asilicon target or silicon compound target that does not contain or onlycontains a small amount of a semi-metallic element), RF sputtering orion beam sputtering is preferably applied. In the case of using a target533 having low electrical conductivity, RF sputtering is applied morepreferably in consideration of deposition rate.

<Mask Blank Manufacturing Procedure>

The method for manufacturing a mask blank according to theaforementioned third embodiment is a method for manufacturing the maskblank 300 of the present disclosure (including variations of the maskblank and to apply similarly hereinafter) previously explained usingFIGS. 7 to 9.

Namely, the method for manufacturing a mask blank of the presentdisclosure is a method for manufacturing the mask blank 300 having thephase-shift film 320 provided on the main surface S of the transparentsubstrate 301 having the concave defect F. In a step of depositing thephase-shift film 320, deposition is carried out by so-called obliqueincidence rotary sputtering that comprises rotating the transparentsubstrate 301 about a rotary axis that passes through the center of themain surface S and arranging the sputtered surface of the sputteringtarget 533 on an angle in opposition to the main surface S having theconcave defect F of the transparent substrate 301.

In this step of depositing the phase-shift film 320, a high transmissionlayer formation step, in which the high transmission layer 322 isdeposited on the main surface S having the concave defect F of thetransparent substrate 301, and a low transmission layer formation step,in which the low transmission layer 321, which has lower transmittancethan the high transmission layer 322, is formed on the high transmissionlayer 322, are carried out by the oblique incidence rotary sputtering.In the high transmission layer 322 formed in the high transmission layerformation step, an internal region of a portion of the high transmissionlayer 322 formed on the concave defect F has the low-density region D,and the density in the low-density region D is relatively lower than thedensity in an internal region of a portion of the high transmissionlayer 322 formed on the main surface S where the concave defect isabsent.

<High Transmission Layer Formation Step and Low Transmission LayerFormation Step>

In the high transmission layer formation step and low transmission layerformation step, reactive sputtering is carried out in a sputtering gascomprising a nitrogen-based gas and a noble gas using the sputteringtarget 533 composed of a material containing silicon. Here, the mixingratio of the nitrogen-based gas in the sputtering gas in the lowtransmission layer formation step in particular is characterized asbeing lower than that of the high transmission layer formation step. Asa result, in the low transmission layer formation step, the nitrogencontent is relatively lower than in the high transmission layer 332deposited in the high transmission layer formation step, and as a resultthereof, the low transmission layer 321 is deposited having loweroptical transmittance than the high transmission layer 322.

Any nitrogen-based gas can be applied for the nitrogen-based gas used assputtering gas in the aforementioned high transmission layer formationstep and low transmission layer formation step if it is a gas thatcontains nitrogen. As was explained in the configuration of the maskblank 300, the oxygen contents of the high transmission layer 322 andthe low transmission layer 321 are preferably held to a low level.Consequently, in order to deposit the high transmission layer 322 andthe low transmission layer 321, a nitrogen-based gas that does notcontain oxygen is applied preferably, and nitrogen gas (N₂ gas) isapplied more preferably.

In addition, a silicon target composed of silicon may be used for thesputtering target 533 containing silicon that is used in the hightransmission layer formation step and low transmission layer formationstep. In addition, in another example, a silicon target containingsilicon and one or more elements selected from semi-metallic elementsand non-metallic elements may be used. As a result, the hightransmission layer 322 and the low transmission layer 321 are depositedcontaining silicon, nitrogen and one or more elements selected fromsemi-metallic elements and non-metallic elements. In this case, one ormore elements selected from boron, germanium, antimony and tellurium arepreferably contained as semi-metallic elements. These semi-metallicelements can be expected to enhance electrical conductivity of thetarget 533. Consequently, in the case of forming the high transmissionlayer 322 and the low transmission layer 321 by DC sputtering inparticular, these semi-metallic elements are preferably contained in thetarget 533. One or more elements selected from carbon, fluorine andhydrogen may also be contained as non-metallic elements.

In the high transmission layer formation step and low transmission layerformation step as previously described, the same sputtering target 533may be used or sputtering targets 533 having different compositions maybe used. However, different sputtering targets 533 are preferably usedto form the low transmission layer 322 and the low transmission layer321 in the high transmission layer formation step and low transmissionlayer formation step. The nitrogen contents are different considerablybetween the low transmission layer 321 and the high transmission layer322, and the mixing ratios of nitrogen-based gas in the sputtering gasduring sputtering and deposition also are different considerably.Consequently, the surface state of the sputtering target 533 duringsputtering and deposition of the low transmission layer 321 and thesurface state of the sputtering target 533 during sputtering anddeposition of the high transmission layer 322 are differentconsiderably. When the low transmission layer 321 is attempted to bedeposited by forming the high transmission layer 322 followed by usingthe sputtering target 533 while in the surface state at that time andchanging the mixing ratio of nitrogen-based gas in the sputtering gas, alarge amount of contaminants are generated from the sputtering target533 and the like, thereby resulting in the risk of a large number ofdefects being formed in the resulting low transmission layer 321. Theuse of different targets 533 to form the low transmission layer 321 andthe high transmission layer 322 eliminates any concern over this andenables the defect quality of the formed film to be enhanced.

In the case of using two different sputtering targets 533 to form thelow transmission layer 321 and the high transmission layer 322, asputtering apparatus configuration can be applied in which twosputtering targets 533 are arranged in a single deposition chamber, or adeposition apparatus configuration can be applied in which twodeposition chambers are provided and one sputtering target 533 isarranged in each deposition chamber. In the case of carrying out thehigh transmission layer formation step and the low transmission layerformation step in different deposition chambers, a configuration ispreferably employed in which each deposition chamber is linked through,for example, a deposition apparatus transfer chamber. As a result, thehigh transmission layer formation step and low transmission layerformation step can be carried out in different deposition chamberswithout exposing the transparent substrate to air.

On the other hand, in the case of forming both the high transmissionlayer 322 and the low transmission layer 321 using a depositionapparatus in which a single sputtering target 533 is arranged in asingle deposition chamber, deposition is carried out on a dummysubstrate after having adjusted the sputtering gas for forming a secondlayer in order optimize the surface state of the sputtering target 533after forming a first layer, and the second layer is then preferablyformed on the first layer. This type of process makes it possible toenhance defect quality of the second layer.

Furthermore, a sputtering target containing silicon and a transitionelement may also be used for the sputtering target 533 containingsilicon used particularly in the low transmission layer formation stepamong the high transmission layer formation step and low transmissionlayer formation step. As a result, a low transmission layer 321 isdeposited that contains silicon, nitrogen and a transition metal.

Moreover, a silicon target is preferably used in each step of thesputtering target 533 that contains silicon used in the hightransmission layer formation step and low transmission layer formationstep. As a result, the high transmission layer 322 and the lowtransmission layer 321 composed of silicon and nitrogen are deposited,and the high transmission layer 322 and the low transmission layer 321have favorable light fastness with respect to exposure light of an ArFexcimer laser and prevent deterioration of optical characteristics overtime.

In addition, in depositing the high transmission layer 322 having ahigher nitrogen content than the low transmission layer 321 in the hightransmission layer formation step in particular, deposition ispreferably carried out by reactive sputtering in the poison mode. In thecase of deposition according to the poison mode, deposition is carriedout by reactive sputtering in which the mixing ratio of nitrogen-basedgas is set to a higher ratio than the range of mixing ratios ofnitrogen-based gas in the transition mode, in which deposition has atendency to be unstable. On the other hand, in depositing the lowtransmission layer 321 having a lower nitrogen content than the hightransmission layer 322 in the low transmission layer formation step,deposition is preferably carried out by reactive sputtering in the metalmode. In the case of deposition according to the metal mode, depositionis carried out by reactive sputtering in which the mixing ratio ofnitrogen-based gas is set to a lower ratio than the range of mixingratios of nitrogen-based gas in the transition mode, in which depositionhas a tendency to be unstable.

As a result, both the high transmission layer 322 and the lowtransmission layer 321 can be deposited by reactive sputtering accordingto deposition conditions for which there are small fluctuations indeposition rate and voltage during deposition. As a result, thephase-shift film 320 can be formed in which uniformity of compositionand optical characteristics is high and defectivity is low.

Furthermore, in the case of laminating a plurality of the laminatedstructures 324 composed of a single layer of the high transmission layer322 and a single layer of the low transmission layer 321 on thetransparent substrate 301, the high transmission layer formation stepand low transmission layer formation step as previously described arerepeatedly carried out in that order. In addition, in the case offabricating a variation of the mask blank 30 as previously described,after having repeated formation of the high transmission layer 322according to the high transmission layer formation step and formation ofthe low transmission layer 321 according to the low transmission layerformation step on the main surface S of the transparent substrate 2 therequired plurality of times, formation of the high transmission layer322 is carried out according to the high transmission layer formationstep.

In addition, in the high transmission layer formation step and lowtransmission layer formation step as previously described, it isnecessary to form the high transmission layer 322 and the lowtransmission layer 321 for which the respective refractive indices n andextinction coefficients k are set to predetermined ranges so that thephase-shift film 320 obtained according to these steps satisfies apredetermined phase difference and a predetermined transmittance withrespect to the exposure light (such as ArF excimer laser light).Consequently, the ratio of a mixed gas of a nitrogen-based gas and anoble gas is adjusted in the high transmission layer formation step andlow transmission layer formation step. In addition, although thepressure of the deposition atmosphere, electrical power applied to thesputtering target 533 and positional relationship such as the distancebetween the sputtering target 533 and the transparent substrate 301 arealso adjusted, since these deposition conditions are inherent to thedeposition apparatus 500, the high transmission layer 322 and the lowtransmission layer 321 formed are suitably adjusted so as to have adesired refractive index n and extinction coefficient k.

<Uppermost Layer Formation Step>

In the case the phase-shift film is provided with the uppermost layer323 formed from a material containing silicon and oxygen at a positionfarthest away from the transparent substrate 301, an uppermost layerformation step is carried out after completion of the high transmissionlayer formation step and low transmission layer formation step. In thisuppermost layer formation step, deposition of the uppermost layer 323 iscarried out by oblique incidence rotary sputtering in continuation fromthe high transmission layer formation step and low transmission layerformation step.

In the uppermost layer formation step, the uppermost layer 323 is formedby reactive sputtering in a sputtering gas comprising nitrogen gas,oxygen gas and a noble gas using the silicon target 533 or a sputteringtarget 533 composed of a material containing one or more elementsselected from semi-metallic elements and non-metallic elements insilicon. This uppermost layer formation step can be applied to formationof the uppermost layer 323 having both configurations, a configurationin which the composition is nearly the same in the direction of layerthickness and a configuration having a composition gradient. Inaddition, in the uppermost layer formation step, the uppermost layer 323may also be formed by reactive sputtering in a sputtering gas comprisinga noble gas and a nitrogen-based gas as necessary using the silicondioxide (SiO₂) target 533 or the target 533 composed of a materialcontaining one or more elements selected from semi-metallic elements andnon-metallic elements in silicon dioxide (SiO₂). This uppermost layerformation step can also be applied to the formation of the uppermostlayer 323 having a configuration in which the composition is nearly thesame in the direction of layer thickness or a configuration having acomposition gradient.

In the case of forming the uppermost layer 323 having a compositiongradient, after having formed a material layer containing silicon andnitrogen by the previously described reactive sputtering, treatmentconsisting of oxidizing at least the surface layer of this materiallayer is additionally carried out. As a result, the uppermost layer 323is formed having a composition gradient in the direction of layerthickness. Examples of treatment used to oxidize the surface layer ofthe material layer in this case include heat treatment in a gascontaining oxygen such as air and treatment in which the uppermost layeris contacted with ozone or oxygen plasma. As a result thereof, theuppermost layer 323 is obtained having a composition gradient in whichthe oxygen content in the layer increases moving away from thetransparent substrate 301. Furthermore, the aforementioned materiallayer containing silicon and nitrogen may also be formed by reactivesputtering under the same deposition conditions as those of the hightransmission layer 322 or the low transmission layer 321.

In addition, as another example of the uppermost layer formation stepused to form the uppermost layer 323 in which the configuration thereofhas a composition gradient, reactive sputtering may be applied in whichthe mixing ratio of each gas component comprising the sputtering gas ischanged in the aforementioned uppermost layer formation step. As aresult, the uppermost layer 323 can be formed having a compositiongradient in the direction of layer thickness. In this case, for example,the mixing ratio of oxygen in the sputtering gas increases as depositionprogresses. As a result, the uppermost layer 323 is obtained that has acomposition gradient such that oxygen content in the layer increasesmoving away from the transparent substrate 301.

In the case the mask blank 300 according to the aforementioned thirdembodiment employs a configuration in which a light shielding film 303is laminated on the phase-shift film 320, a light shielding filmformation step is carried out after having formed the phase-shift film320. In addition, in the case the mask blank 300 has a configuration inwhich the etching mask film 304 is laminated on the light shielding film303, an etching mask film formation step is carried out after the lightshielding film formation step. There are no limitations on therespective deposition methods used in the light shielding film formationstep and etching mask film formation step, and a sputtering method, forexample, is applied. Moreover, in the case the mask blank 300 has aconfiguration in which the resist film 305 is laminated on the etchingmask film 304, a resist film formation step is carried out after theetching mask film formation step. A spin coating method, for example, isapplied for the resist film formation step.

<<Phase-Shift Mask>>

FIG. 10 is a cross-sectional view showing the configuration of aphase-shift mask according to the third embodiment. As shown in thisdrawing, a phase-shift mask 600 is characterized in that a transferpattern 350 is formed on the phase-shift film 320 in the mask blank 300according to the aforementioned third embodiment. Furthermore, althougha configuration in which the transfer mask 350 is formed on thephase-shift film 320 of the mask blank 300 explained using FIG. 7 isexplained using the example of FIG. 10, a transfer mask is similarlyformed on a phase-shift film in the previously described variations ofthe mask blank as well.

Namely, the phase-shift mask 600 has the transfer pattern 350, obtainedby patterning the phase-shift film 320, in a transfer pattern formationregion 303 a in the central portion of the transparent substrate 301. Inaddition, an outer peripheral region 303 b of the transfer patternformation region 303 a is covered with the light shielding film 303remaining on the upper portion of the phase-shift film 320. Inparticular, a configuration is employed so as not to arrange the concavedefect F in the transparent substrate 301 in the region where a finetransfer pattern (utilizing phase shift) of the transfer pattern 350 isformed. Namely, a configuration is employed in which the concave defectF is covered by a transfer pattern 320 a composed of a large-areaphase-shift film.

Here, a low-density region (not shown), having a density lower than thesurrounding region as previously described, is present in the hightransmission layer 322 in the phase-shift film 320 of the upper portionof this concave defect F, the high transmission layer 322 being on theclosest side to the transparent substrate 301. However, since the hightransmission layer 322 inherently has high transmittance, even if thishigh transmission layer 322 is formed at low density, the degree ofincrease in overall transmittance in the direction of film thickness ofthe phase-shift film attributable thereto is low. Consequently, in thephase-shift mask 600 having this phase-shift film 320, the effect of thelow-density region on pattern exposure and transfer can be held to a lowlevel. In addition, even if the transfer pattern 320 a on this concavedefect F has amount of phase-shift that is out of the setting value dueto the presence of this low-density region, there is no effect on theformation of a fine exposure pattern by pattern exposure using thisphase-shift mask 600.

<<Method for Manufacturing Phase-Shift Mask>>

The method for producing the phase-shift mask 600 according to the thirdembodiment is characterized by having a step of forming the transferpattern 350 on the phase-shift film 320 of the mask blank 300manufactured using the aforementioned manufacturing method. This methodfor manufacturing the phase-shift mask 600 according to the thirdembodiment differs from the method for manufacturing a phase-shift maskaccording to the aforementioned first embodiment in that, when exposingand drawing a transfer pattern to be formed on the phase-shift film 320(phase-shift pattern) in the form of a first pattern on a resist film, apattern design is employed in which the concave defect F of thetransparent substrate 301 is covered with a first resist pattern thatdoes not utilize phase shift. Other matters are the same as those of themethod for manufacturing a phase-shift mask according to theaforementioned first embodiment.

<<Method for Manufacturing a Semiconductor Device>>

The method for manufacturing a semiconductor device according to thethird embodiment is characterized in that a transfer pattern of aphase-shift mask is exposed and transferred to a resist film on asubstrate using the phase-shift mask according to the aforementionedthird embodiment or a phase-shift mask manufactured using the mask blankaccording to the aforementioned third embodiment. Other matters are thesame as those of the method for manufacturing a semiconductor deviceaccording to the aforementioned first embodiment.

EXAMPLES

The following provides a more detailed explanation of the firstembodiment of the present disclosure according to Examples 1-1 and 1-2and Comparative Example 1-1.

Example 1-1

<<Manufacturing of Mask Blank>>

The transparent substrate 1 composed of synthetic quartz glass wasprepared in which dimensions of the main surface were about 152 mm×about152 mm and thickness was about 6.25 mm. This transparent substrate 1 waspolished to a predetermined surface roughness for the edge faces andmain surface followed by subjecting to predetermined cleaning treatmentand drying treatment.

Next, the transparent substrate 1 was placed in a single-wafer RFsputtering apparatus, and the low transmission layer 21, composed ofsilicon and nitrogen (Si:N=59 at %:41 at %), was formed at a thicknessof 12 nm on the transparent substrate 1 by reactive sputtering (RFsputtering) using a silicon (Si) target by using a mixed gas of argon(Ar) and nitrogen (N₂) (flow rate ratio Ar:N₂=2:3, pressure=0.035 Pa)for the sputtering gas, and setting the electrical power of the RF powersupply to 2.8 kW. When only the low transmission layer 21 was formedunder the same conditions on a main surface of a different transparentsubstrate and optical characteristics of this low transmission layer 21were measured using a spectroscopic ellipsometer (M-2000D, J. A. WoollamCo., Inc.), refractive index n at a wavelength of 193 nm was 1.85 andextinction coefficient k was 1.70. Furthermore, conditions used whendepositing this low transmission layer 21 were such that depositionconditions such as flow rate ratio were selected that allowed stabledeposition in the metal mode region by preliminarily verifying therelationship between deposition rate and flow rate ratio of N₂ gas in amixed gas of Ar gas and N₂ gas in the sputtering gas with thesingle-wafer RF sputtering apparatus used. Furthermore, the compositionof the low transmission layer 21 was obtained by measurement using X-rayphotoemission spectroscopy (XPS). This applies similarly with respect toother films as well.

Next, the transparent substrate 1 laminated with the low transmissionlayer 21 was installed in the single-wafer RF sputtering apparatus, andthe high transmission layer 22, composed of silicon and nitrogen(Si:Ni=46 at %:54 at %), was formed at a thickness of 55 nm on the lowtransmission layer 21 by reactive sputtering (RF sputtering) using asilicon (Si) target, using a mixed gas of argon (Ar) and nitrogen (N₂)(flow rate ratio Ar:N₂=1:3, pressure=0.09 Pa) for the sputtering gas,and setting the electrical power of the RF power supply to 2.8 kW. Whenonly the high transmission layer 22 was formed on a main surface of adifferent transparent substrate and optical characteristics of this hightransmission layer 22 were measured using a spectroscopic ellipsometer(M-2000D, J. A. Woollam Co., Inc.), refractive index n at a wavelengthof 193 nm was 2.52 and extinction coefficient k was 0.39. Furthermore,conditions used when depositing this high transmission layer 22 weresuch that deposition conditions such as flow rate ratio were selectedthat allowed stable deposition in the reaction mode (poison mode) regionby preliminarily verifying the relationship between deposition rate andflow rate ratio of N₂ gas in a mixed gas of Ar gas and N₂ gas in thesputtering gas with the single-wafer RF sputtering apparatus used.

Next, the transparent substrate 1 laminated with the low transmissionlayer 21 and the high transmission layer 22 was installed in thesingle-wafer RF sputtering apparatus, and the uppermost layer 23,composed of silicon and oxygen, was formed at a thickness of 4 nm on thehigh transmission layer 22 by reactive sputtering (RF sputtering) usinga silicon dioxide (SiO₂) target, using argon (Ar) gas (pressure=0.03 Pa)for the sputtering gas, and setting the electrical power of the RF powersupply to 1.5 kW. Furthermore, when only the uppermost layer 23 wasformed on a main surface of a different transparent substrate andoptical characteristics of this uppermost layer 23 were measured using aspectroscopic ellipsometer (M-2000D, J. A. Woollam Co., Inc.),refractive index n at a wavelength of 193 nm was 1.56 and extinctioncoefficient k was 0.00.

According to the aforementioned procedure, the phase-shift film 2,composed of the low transmission layer 21, the high transmission layer22 and the uppermost layer 23, was formed on the transparent substrate1. When transmittance and phase difference were measured for thisphase-shift film 2 at the wavelength of light of an ArF excimer laser(about 193 nm) with a phase shift measuring apparatus, transmittance was5.97% and phase difference was 177.7 degrees.

Next, the transparent substrate 1 having the phase-shift film 2 formedthereon was installed in a single-wafer DC sputtering apparatus, and thelowermost layer of the light shielding film 3 composed of CrOCN wasformed at a thickness of 30 nm on the phase-shift film 2 by reactivesputtering (DC sputtering) using a chromium (Cr) target, using a mixedgas of argon (Ar), carbon dioxide (CO₂), nitrogen (N₂) and helium (He)(flow rate ratio Ar:CO₂:N₂:He=22:39:6:33, pressure: 0.2 Pa) for thesputtering gas, and setting the electrical power of the DC power supplyto 1.9 kW.

Next, the lower layer of the light shielding film 3 composed of CrN wasformed at a thickness of 4 nm on the phase-shift film 2 by reactivesputtering (DC sputtering) using the same chromium (Cr) target, using amixed gas of argon (Ar) and nitrogen (N₂) (flow rate ratio Ar:N₂=83:17,pressure=0.1 Pa) for the sputtering gas, and setting the electricalpower of the DC power supply to 1.4 kW.

Next, the upper layer of the light shielding film 3 composed of CrOCNwas formed at a thickness of 14 nm on the phase-shift film 2 by reactivesputtering (DC sputtering) using the same chromium (Cr) target, using amixed gas of argon (Ar), carbon dioxide (CO₂), nitrogen (N₂) and helium(He) (flow rate ratio Ar:CO₂:N₂:He=21:37:11:31, pressure=0.2 Pa) for thesputtering gas, and setting the electrical power of the DC power supplyto 1.9 kW. According to the aforementioned procedure, the lightshielding film 3 of a chromium-based material, composed of a three-layerstructure consisting a lowermost layer composed of CrOCN, a lower layercomposed of CrN and upper layer composed of CrOCN starting from the sideof the phase-shift film 2, was formed at a total film thickness of 48nm.

Moreover, the transparent substrate 1 laminated with the phase-shiftfilm 2 and the light shielding film 3 was installed in a single-wafer RFsputtering apparatus, and the etching mask film 4, composed of siliconand oxygen, was formed at a thickness of 5 nm on the light shieldingfilm 3 by RF sputtering using a silicon dioxide (SiO₂) target, usingargon (Ar) gas (pressure: 0.03 Pa) for the sputtering gas, and settingthe electrical power of the RF power supply to 1.5 kW. According to theaforementioned procedure, the mask blank 100 was manufactured providedwith a structure obtained by laminating the phase-shift film 2 having athree-layer structure, the light shielding film 3 and the etching maskfilm 4 on the transparent substrate 1.

<<Manufacturing of Phase-Shift Mask>

Next, the phase-shift mask 200 of Example 1-1 was fabricated accordingto the following procedure using the mask blank 100 of Example 1-1.First, HMDS treatment was carried out on the surface of the etching maskfilm 4. Continuing, a resist film composed of a chemically amplifiedresist for electron beam drawing was formed at a film thickness of 80 nmin contact with the surface of the etching mask film 4 by spin coating.Next, a phase-shift pattern to be formed on the phase-shift film in theform of a first pattern was drawn with an electron beam on this resistfilm followed by carrying out a predetermined cleaning treatment anddrying treatment to form a first resist pattern 5 a having the firstpattern (see FIG. 3A).

Next, dry etching using CF₄ gas was carried out using the first resistpattern 5 a as a mask to form the first pattern (etching mask pattern 4a) on the etching mask film 4 (see FIG. 3B).

Next, the first resist pattern 5 a was removed. Continuing, dry etchingusing a mixed gas of chlorine and oxygen (gas flow rate ratioCl₂:O₂=4:1) was carried out using the etching mask pattern 4 a as a maskto form the first pattern (light shielding pattern 3 a) on the lightshielding film 3 (see FIG. 3C).

Next, dry etching using a fluorine-based gas (SF₆+He) was carried outusing the light shielding pattern 3 a as a mask to form the firstpattern (phase-shift pattern 2 a) on the phase-shift film 2 whilesimultaneously removing the etching mask pattern 4 a (see FIG. 3D).

Next, a resist film composed of a chemically amplified resist forelectron beam drawing was formed at a film thickness of 150 nm on thelight shielding film pattern 3 a by spin coating. Next, a pattern to beformed on the light shielding film (light shielding pattern) in the formof a second pattern was exposed and drawn on the resist film followed byfurther carrying out a predetermined treatment such as developingtreatment to form the second resist pattern 6 b having a light shieldingpattern. Continuing, dry etching using a mixed gas of chlorine andoxygen (gas flow rate ratio Cl₂:O₂=4:1) was carried out using the secondresist pattern 6 b as a mask to form the second pattern (light shieldingpattern 3 b) on the light shielding film 3 (see FIG. 3E). Moreover, thesecond resist pattern 6 b was removed following by going throughpredetermined treatment such as cleaning to obtain the phase-shift mask200 (see FIG. 3F).

When a mask pattern inspection was carried out with a mask inspectionapparatus on the halftone phase-shift mask 200 fabricated in Example1-1, it was confirmed that a fine pattern was formed within theacceptable range of the design value. Next, treatment was carried out onthe phase-shift pattern of this halftone phase-shift mask 200 of Example1-1 by irradiating with ArF excimer laser light at a cumulative dose of20 kJ/cm². The change in CD of the phase-shift pattern before and afterthis radiation treatment was about 2 nm, and this amount of change in CDwas within a usable range as a phase-shift mask.

A simulation of a transferred image was carried out on the halftonephase-shift mask 200 of Example 1-1 after undergoing radiation treatmentwith ArF excimer laser light when exposed and transferred to a resistfilm on a semiconductor device with exposure light having a wavelengthof 193 nm using the AIMS193 (Carl Zeiss AG). When this simulated exposedand transferred image was verified, it was determined to adequatelysatisfy design specifications. On the basis of this result, even if thephase-shift mask of Example 1-1 is placed on the mask stage of anexposure apparatus after being irradiated with an ArF excimer laser at acumulative dose of 20 kJ/cm² and exposed and transferred to a resistfilm on a semiconductor device, it can be said that the circuit patternultimately formed on the semiconductor device can be formed with highprecision.

Example 1-2

<<Manufacturing of Mask Blank>>

The transparent substrate 1 was prepared in the same manner as Example1-1. Next, the transparent substrate 1 was placed in a single-wafer RFsputtering apparatus and the high transmission layer 22 was formed underthe same deposition conditions as those of the high transmission layer22 of Example 1-1 with the exception of changing the thickness to 18 nm.The optical characteristics of this high transmission layer 22 were thesame as those of the high transmission layer 22 of Example 1-1 in thatthe refractive index n at a wavelength of 193 nm was 2.52 and theextinction coefficient was 0.39.

Next, the transparent substrate 1 laminated with the high transmissionlayer 22 was installed in the single-wafer RF sputtering apparatus andthe low transmission layer 21 was formed under the same depositionconditions as those of the low transmission layer 21 of Example 1-1 withthe exception of changing the thickness to 7 nm. The opticalcharacteristics of this low transmission layer 21 were the same as thoseof the low transmission layer 21 of Example 1-1 in that the refractiveindex n at a wavelength of 193 nm was 1.85 and the extinctioncoefficient was 1.70.

Next, the transparent substrate 1 laminated with the high transmissionlayer 22 and the low transmission layer 21 was installed in thesingle-wafer RF sputtering apparatus, and the high transmission layer 22was formed under the same deposition conditions as those of the hightransmission layer 22 of Example 1-1 with the exception of changing thethickness to 18 nm. The optical characteristics of this hightransmission layer 22 were the same as those of the high transmissionlayer 22 of the first layer.

Next, the transparent substrate 1 laminated with the high transmissionlayer 22, the low transmission layer 21 and the high transmission layer22 in that order was installed in the single-wafer RF sputteringapparatus and the low transmission layer 21 was formed under the samedeposition conditions as those of the low transmission layer 21 ofExample 1-1 with the exception of changing the thickness to 7 nm. Theoptical characteristics of this low transmission layer 21 were the sameas those of the low transmission layer 21 of the second layer.

Next, the transparent substrate 1 laminated with the high transmissionlayer 22, the low transmission layer 21, the high transmission layer 22and the low transmission layer 21 in that order was installed in thesingle-wafer RF sputtering apparatus and the uppermost layer 23 wasformed under the same deposition conditions as those of the hightransmission layer 22 of Example 1-1 with the exception of changing thethickness to 18 nm. At this point, the optical characteristics of theuppermost layer 23 were the same as those of the high transmission layer22 of the first layer. Next, oxidizing treatment using ozone was carriedout on the uppermost layer 23 on the transparent substrate to form anoxidized layer on the surface layer of the uppermost layer 23. As aresult, a composition gradient film was obtained for the uppermost layerin which oxygen content tended to increase moving away from the side ofthe transparent substrate.

According to the aforementioned procedure, the phase-shift film 2 havinga five-layer structure, composed of the high transmission layer 22, thelow transmission layer 21, the high transmission layer 22, the lowtransmission layer 21 and the uppermost layer 23, was formed on thetransparent substrate 1. When transmittance and phase difference weremeasured for this phase-shift film 2 at the wavelength of light of anArF excimer laser (about 193 nm) with a phase shift measuring apparatus,transmittance was 5.91% and phase difference was 181.2 degrees.

Next, the light shielding film 3 of a chromium-based material composedof a three-layer structure was formed at a thickness of 48 nm on thephase-shift film 2 using the same procedure as that of Example 1-1.Continuing, the etching mask film composed of silicon and oxygen wasformed at a thickness of 5 nm on the light shielding film 3 using thesame procedure as that of Example 1-1. According to the aforementionedprocedure, the mask blank 101 of Example 1-2 was manufactured providedwith a structure obtained by laminating the phase-shift film 2 having afive-layer structure, the light shielding film 3 and the etching maskfilm 4 on the transparent substrate 1.

<<Manufacturing of Phase-Shift Mask>>

Next, the phase-shift mask 200 of Example 1-2 was fabricated accordingto the same procedure as Example 1-1 using this mask blank 101 ofExample 1-2. When a mask pattern inspection was carried out with a maskinspection apparatus on the halftone phase-shift mask 200 fabricated inExample 1-2, it was confirmed that a fine pattern was formed within theacceptable range of the design value. Next, treatment was carried out onthe phase-shift pattern of this halftone phase-shift mask 200 of Example1-2 by irradiating with ArF excimer laser light at a cumulative dose of20 kJ/cm². The change in CD of the phase-shift pattern before and afterthis radiation treatment was about 2 nm, and this amount of change in CDwas within a usable range as a phase-shift mask.

A simulation of a transferred image was carried out on the halftonephase-shift mask 200 of Example 1-2 after undergoing radiation treatmentwith ArF excimer laser light when exposed and transferred to a resistfilm on a semiconductor device with exposure light having a wavelengthof 193 nm using the AIMS193 (Carl Zeiss AG). When this simulated exposedand transferred image was verified, it was determined to adequatelysatisfy design specifications. On the basis of this result, even if thephase-shift mask of Example 1-2 is placed on the mask stage of anexposure apparatus after being irradiated with an ArF excimer laser at acumulative dose of 20 kJ/cm² and then exposed and transferred to aresist film on a semiconductor device, it can be said that the circuitpattern ultimately formed on the semiconductor device can be formed withhigh precision.

Comparative Example 1-1

<<Manufacturing of Mask Blank>>

A transparent substrate composed of synthetic quartz glass, in whichdimensions of the main surface were about 152 mm×about 152 mm andthickness was about 6.25 mm, was prepared using the same procedure as inthe case of Example 1-1. Next, the transparent substrate was installedin a single-wafer DC sputtering apparatus, and a phase-shift film,composed of molybdenum, silicon and nitrogen, was formed at a thicknessof 69 nm on the transparent substrate 1 by reactive sputtering (DCsputtering) using a mixed sintered target of molybdenum (Mo) and silicon(Si) (Mo:Si=12 at %: 88 at %), and using a mixed gas of argon (Ar),nitrogen (N₂) and helium (He) (flow rate ratio Ar:N₂:He=8:72:100,pressure=0.2 Pa) for the sputtering gas.

Next, heat treatment in air was carried out on the phase-shift film onthe transparent substrate. This heat treatment was carried out for 1hour at 450° C. When transmittance and phase difference were measuredfor this phase-shift film of Comparative Example 1-1, after heattreatment, at the wavelength of light of an ArF excimer laser (about 193nm) with a phase shift measuring apparatus, transmittance was 6.02% andphase difference was 177.9 degrees.

Next, a light shielding film of a chromium-based material composed of athree-layer structure was formed at a total film thickness of 48 nm onthe phase-shift film using the same procedure as Example 1-1.Continuing, an etching mask film composed of silicon and oxygen wasformed at a thickness of 5 nm on the light shielding film using the sameprocedure as Example 1-1. According to the aforementioned procedure, themask blank of Comparative Example 1-1 was manufactured provided with astructure obtained by laminating a phase-shift film composed of MoSiN, alight shielding film and an etching mask film on a transparentsubstrate.

<<Manufacturing of Phase-Shift Mask>>

Next, a phase-shift mask of Comparative Example 1-1 was fabricatedaccording to the same procedure as Example 1-1 using this mask blank ofComparative Example 1-1. When a mask pattern inspection was carried outwith a mask inspection apparatus on the halftone phase-shift maskfabricated in Comparative Example 1-1, it was confirmed that a finepattern was formed within the acceptable range of the design value.Next, treatment was carried out on the phase-shift pattern of thishalftone phase-shift mask of Comparative Example 1-1 by irradiating withArF excimer laser light at a cumulative dose of 20 kJ/cm². The change inCD of the phase-shift pattern before and after this radiation treatmentwas not less than 20 nm, and this amount of change in CD exceeded therange that allows use as a phase-shift mask.

A simulation of a transferred image was carried out on the halftonephase-shift mask 200 of Comparative Example 1-1 after undergoingradiation treatment with ArF excimer laser light when exposed andtransferred to a resist film on a semiconductor device with exposurelight having a wavelength of 193 nm using the AIMS193 (Carl Zeiss AG).When this simulated exposed and transferred image was verified, it wasunable to satisfy design specifications due to the effect of the changein CD of the phase-shift pattern. On the basis of this result, in thecase the phase-shift mask of Comparative Example 1-1 is placed on themask stage of an exposure apparatus after being irradiated with an ArFexcimer laser at a cumulative dose of 20 kJ/cm² and exposed andtransferred to a resist film on a semiconductor device, circuit patterndisconnections and short-circuits are expected to occur in a circuitpattern ultimately formed on the semiconductor device.

The following provides a more detailed explanation of the secondembodiment of the present disclosure according to Examples 2-1 and 2-2and Comparative Examples 2-1 and 2-2.

Example 2-1

<<Manufacturing of Mask Blank>>

The present disclosure is explained with reference to FIGS. 1, 5 and 6.FIG. 1 is a cross-sectional view showing the mask blank of the presentExample. FIG. 5 is a flow chart showing the manufacturing process of thephotomask blank of the present Example. FIG. 6 is a schematic diagramshowing the configuration of an RF sputtering apparatus used to deposita phase-shift film.

As shown in the flow chart of FIG. 5, the method for manufacturing themask blank 100 of the present Example employs a procedure mainlyconsisting of preparation of a transparent substrate (S1), formation ofa phase-shift film (S2), formation of a light shielding film (S3) andformation of an etching mask (S4). The step of forming a phase-shiftfilm (S2) comprises steps for the formation of a low transmission layer(S21), formation of a high transmission layer (S22) and formation of anoxidized layer (S23). The following provides a detailed description ofeach step.

(Preparation of Transparent Substrate 1: Step S1)

First, the transparent substrate 1 used in the mask blank is prepared. Asynthetic quartz glass substrate having surface dimensions of about 152mm×about 152 mm and having a thickness of about 6.35 mm was prepared foruse as the transparent substrate 1. This transparent substrate 1 waspolished to a predetermined surface roughness for the edge faces andmain surface followed by subjecting to predetermined cleaning treatmentand drying treatment.

(Deposition of Phase-Shift Film: Step S2)

Next, deposition of the phase-shift film 2 was carried out (S2). Thephase-shift film 2 was deposited using a single-wafer RF sputteringapparatus 30 shown in the schematic diagram of FIG. 6. An explanation isfirst provided of the single-wafer RF sputtering apparatus 30 withreference to FIG. 6.

The single-wafer RF sputtering apparatus 30 is provided with a vacuumchamber 32 where sputtering is carried out. The vacuum chamber 32 isconnected to a vacuum pump 36 for evacuating the inside of the vacuumchamber 32 through a main valve 34.

The sputtering apparatus 30 is provided with an inert gas inlet line 42,which enables an inert gas to be introduced into the vacuum chamber 32,and a reactive gas inlet line 46, which enables a reactive gas to beintroduced into the vacuum chamber 32. The inert gas inlet line 42communicates with an inert gas supply source 40, and the reactive gasinlet line communicates with a reactive gas supply source 44. Theseinlet lines 42 and 46 are provided with mass flow controllers, variousvalves and the like (not shown) between these lines 42, 46 and the gassupply sources 40, 44. Furthermore, in the Example, the inert gas isargon and the reactive gas is nitrogen. In addition, pressure inside thevacuum chamber 32 is measured by a pressure gauge 48.

Inside the pressure chamber 32, two targets 55, 65, in which thesurfaces of the target material are exposed, are held in target holders52, 62 through backing plates 53, 63. In addition, a substrate holder 35for holding a deposited surface of the transparent substrate 1 facingupward is provided at a predetermined position where sputteringparticles emitted from the targets 55, 65 arrived at. The substrateholder 35 is connected to a rotating mechanism (not shown) and isconfigured so as to enable the deposited surface of the transparentsubstrate to rotate in the horizontal plane during sputtering.

The target 55 and the target 65 are provided above and on an angle withrespect to the deposited surface of the transparent substrate 1. RFpower supplies 52, 62, which apply electrical power for sputterdischarge, are connected to the target holders 52, 62 through impedancematching transformers (not shown). Sputtering is carried out as a resultof the formation of plasma when electrical power is applied to thetargets 55, 65 from the power supplies 50 and 60. The target holders 52,62 are insulated from the vacuum chamber 32 by insulators. The targetholders 52, 62 are made of metal and serve as electrodes in the caseelectrical power is applied thereto.

The targets 55, 65 are composed of raw materials of a thin film formedon the substrate. In the present Example, the targets 55, 65 are bothsilicon targets. The target holders 52, 62 are placed in cylindricalchambers 56, 66 within the vacuum chamber 32. As a result of housing thetarget holders 52, 62 in these cylindrical chambers 56, 66, whensputtering is carried out using one of the targets 55, 65, sputteringparticles are prevented from adhering to the other of the targets 55,65.

Next, an explanation is provided of a specific method for manufacturingthe phase-shift film 2.

(Formation of Low Transmission Layer 21: Step S21)

First, the transparent substrate 1 was installed on the substrate holder35 in the single-wafer RF sputtering apparatus 30 with the surfacefacing upward, followed by deposition of the low transmission layer 21(Step S21). The low transmission layer 21 was formed by RF sputteringusing the silicon (Si) target 55. A mixed gas of an inert gas in theform of argon (Ar) gas and a reactive gas in the form of nitrogen (N₂)gas was used for the sputtering gas. The flow rate ratio and otherdeposition conditions that allowed stable deposition in the region ofthe metal mode were selected by preliminary verifying the relationshipbetween deposition rate and flow rate ratio of N₂ gas in the mixed gasof Ar gas and N₂ gas in the sputtering gas in the RF sputteringapparatus 30. In the present Example, deposition was carried out at aflow rate ratio of the mixed gas of Ar:N₂=2:3 and a pressure within thevacuum chamber 32 of 0.035 Pa. The flow rate of the mixed gas wascontrolled with a mass flow controller provided in the inert gas inletline 42 and a mass flow controller provided in the reactive gas inletline 46. While in this state, discharge was initiated by applyingelectrical power of 2.8 kW from the RF power supply to the target 55 toform the low transmission layer 21 composed of silicon and nitrogen(Si:N=59 at %:41 at %) at a thickness of 12 nm on the transparentsubstrate 1.

When only the low transmission layer 21 was then formed on a mainsurface of a different transparent substrate under the same conditionsand optical characteristics of the low transmission layer 21 weremeasured using a spectroscopic ellipsometer (M-2000D, J. A. Woollam Co.,Inc.), refractive index n at a wavelength of 193 nm was 1.85 andextinction coefficient k was 1.70.

(Formation of High Transmission Layer 22: Step S22)

Next, the sputtering gas conditions in the vacuum chamber 32 werechanged to the poison mode followed by formation of the hightransmission layer 22 on the surface of the low transmission layer 21(Step S22). Formation of the high transmission layer 22 was carried outcontinuously after formation of the low transmission layer 21. The hightransmission layer 22 was formed by RF sputtering using the silicon (Si)target 65.

A mixed gas of an inert gas in the form of argon (Ar) gas and a reactivegas in the form of nitrogen (N₂) gas was used for the sputtering gas.The flow rate ratio and other deposition conditions that allowed stabledeposition in the region of the poison mode were selected by preliminaryverifying the relationship between deposition rate and flow rate ratioof N₂ gas in the mixed gas of Ar gas and N₂ gas in the sputtering gas inthe RF sputtering apparatus 30. In the present Example, deposition wascarried out at a flow rate ratio of the mixed gas of Ar:N₂=1:3 and apressure within the vacuum chamber 32 of 0.090 Pa. The flow rate of themixed gas was controlled with a mass flow controller provided in theinert gas inlet line 42 and a mass flow controller provided in thereactive gas inlet line 46. While in this state, discharge was initiatedby applying electrical power of 2.8 kW from the RF power supply to thetarget 65 to form the high transmission layer 22 composed of silicon andnitrogen (Si:N=46 at %:54 at %) at a thickness of 55 nm on thetransparent substrate 1.

When only the high transmission layer 22 was then formed on a mainsurface of a different transparent substrate under the same conditionsand optical characteristics of the high transmission layer 22 weremeasured using a spectroscopic ellipsometer (M-2000D, J. A. Woollam Co.,Inc.), refractive index n at a wavelength of 193 nm was 2.52 andextinction coefficient k was 0.39.

(Formation of Oxidized Layer 23: Step S23)

Next, the transparent substrate 1 laminated with the low transmissionlayer 21 and the high transmission layer 22 was installed in the vacuumchamber of a different RF sputtering apparatus from the single-wafer RFsputtering apparatus 30, and the oxidized layer (uppermost layer) 23,composed of silicon and oxygen, was formed at a thickness of 4 nm on thehigh transmission layer 22 by RF sputtering using a silicon dioxide(SiO₂) target, using argon (Ar) gas (pressure=0.03 Pa) for thesputtering gas, and setting the electrical power of the RF power supplyto 1.5 kW. Furthermore, when only the oxidized layer 23 was then formedon a main surface of a different transparent substrate under the sameconditions and optical characteristics of the oxidized layer 23 weremeasured using a spectroscopic ellipsometer (M-2000D, J. A. Woollam Co.,Inc.), refractive index n at a wavelength of 193 nm was 1.56 andextinction coefficient k was 0.00.

According to the aforementioned procedure, a phase-shift film 2,composed of the low transmission layer 21, the high transmission layer22 and the oxidized layer 23, was formed on the transparent substrate 1.When transmittance and phase difference were measured for thisphase-shift film 2 at the wavelength of light of an ArF excimer laser(about 193 nm) with a phase shift measuring apparatus, transmittance was5.97% and phase difference was 177.7 degrees.

(Formation of Light Shielding Film: Step S3)

Next, the light shielding film 3, having a three-layer structurecomposed of a lowermost layer, lower layer and upper layer, was formedon the phase-shift film 2 according to the same procedure as that ofExample 1-1.

(Formation of Etching Mask Film: Step S4)

Next, the etching mask film 4 was formed on the surface of the lightshielding film 3 according to the same procedure as that of Example 1-1.

According to the aforementioned procedure, the mask blank 100 of Example2-1 was manufactured provided with a structure obtained by laminatingthe phase-shift film 2, having a three-layer structure composed of thelow transmission layer 21, the high transmission layer 22 and theoxidized layer 23, the light shielding film 3 and the etching mask film4 on the transparent substrate 1.

<<Manufacturing of Phase-Shift Mask>>

The phase-shift mask 200 was fabricated according to the same procedureas that of Example 1-1 using this mask blank 100 of Example 2-1.

When a mask pattern inspection was carried out with a mask inspectionapparatus on the halftone phase-shift mask 200 fabricated in Example2-1, it was confirmed that a fine pattern corresponding to the DRAM hp32nm generation was formed within the acceptable range of the designvalue. Next, treatment was carried out on the phase-shift pattern 2 a ofthis halftone phase-shift mask 200 of Example 2-1 by irradiating withArF excimer laser light at a cumulative dose of 20 kJ/cm². The change inCD of the phase-shift pattern 2 a before and after this radiationtreatment was about 2 nm, and this amount of change in CD was within ausable range as a phase-shift mask.

A simulation of a transferred image was carried out on the halftonephase-shift mask 200 of Example 2-1 after undergoing radiation treatmentwith ArF excimer laser light when exposed and transferred to a resistfilm on a semiconductor device with exposure light having a wavelengthof 193 nm using the AIMS193 (Carl Zeiss AG). When this simulated exposedand transferred image was verified, it was determined to adequatelysatisfy design specifications. On the basis of this result, even if thephase-shift mask of Example 2-1 is placed on the mask stage of anexposure apparatus after being irradiated with an ArF excimer laser at acumulative dose of 20 kJ/cm² and exposed and transferred to a resistfilm on a semiconductor device, it can be said that the circuit patternultimately formed on the semiconductor device can be formed with highprecision.

Example 2-2

The following provides an explanation of the mask blank 101 of Example2-2 with reference to FIG. 2. FIG. 2 is a schematic cross-sectional viewshowing the configuration of the mask blank 101 of the present Example.Furthermore, since Example 2-2 is the same as Example 2-1 with theexception of the configuration of the phase-shift film 2, duplicateexplanations are omitted.

<<Manufacturing of Mask Blank>>

The same transparent substrate as Example 2-1 was prepared using thesame procedure as that of Example 2-1. Next, the phase-shift film 2 wasformed using the single-wafer RF sputtering apparatus 30. Thesingle-wafer RF sputtering device 30 is the same as the apparatus usedin Example 2-1 (see FIG. 6).

First, the transparent substrate 1 was installed in the RF sputteringapparatus 30 on the substrate holder 35 with the surface facing upward.Next, the high transmission layer 22 was formed at a film thickness of18 nm under deposition conditions of the poison mode in the same manneras the high transmission layer 22 of Example 2-1. The opticalcharacteristics of this high transmission layer 22 were the same asthose of the high transmission layer 22 of Example 2-1 in that therefractive index n at a wavelength of 193 nm was 2.52 and the extinctioncoefficient was 0.39.

Next, the low transmission layer 21 was formed at a film thickness of 7nm under deposition conditions of the metal mode in the same manner asthe low transmission layer 21 of Example 2-1. The opticalcharacteristics of this low transmission layer 21 were the same as thoseof the low transmission layer 21 of Example 2-1 in that the refractiveindex n at a wavelength of 193 nm was 1.85 and the extinctioncoefficient was 1.70.

Next, the high transmission layer 22 was formed at a film thickness of18 nm under deposition conditions of the poison mode in the same manneras the high transmission layer 22 of Example 2-1. The opticalcharacteristics of this high transmission layer 22 were the same asthose of the high transmission layer 22 of the first layer.

Next, the low transmission layer 21 was formed at a film thickness of 7nm under deposition conditions of the metal mode in the same manner asthe low transmission layer 21 of Example 2-1. The opticalcharacteristics of this low transmission layer 21 were the same as thoseof the low transmission layer 21 of the second layer.

Next, a silicon nitride layer was formed at a thickness of 18 nm underconditions of the poison mode in the same manner as the hightransmission layer 22 of Example 2-1. Next, oxidation treatment usingozone was carried out on the uppermost side in the form of the siliconnitride layer to form the oxidized layer (uppermost layer) 23 on thesurface layer.

According to the aforementioned procedure, a phase-shift film 2, havinga five-layer structure composed of the high transmission layer 22, thelow transmission layer 21, the high transmission layer 22, the lowtransmission layer 21 and the oxidized layer 23, was formed on thetransparent substrate 1. When transmittance and phase difference weremeasured for this phase-shift film 2 at the wavelength of light of anArF excimer laser (about 193 nm) with a phase shift measuring apparatus(capable of also measuring transmittance), transmittance was 5.91% andphase difference was 181.2 degrees.

Next, the light shielding film 3 of a chromium-based material composedof a three-layer structure was formed at a total film thickness of 48 nmon the phase-shift film 2 according to the same procedure as that ofExample 1-1. Continuing, the etching mask film 4, composed of siliconand oxygen, was formed at a thickness of 5 nm on the light shieldingfilm 3 according to the same procedure as that of Example 1-1. Accordingto the aforementioned procedure, the mask blank 101 of Example 2-2 wasmanufactured provided with a structure obtained by laminating thephase-shift film 2 having a five-layer structure, the light shieldingfilm 3 and the etching mask film 4 on the transparent substrate 1.

<<Manufacturing of Phase-Shift Mask>>

The phase-shift mask 200 of Example 2-2 was fabricated according to thesame procedure as that of Example 1-1 using this mask blank 101 ofExample 2-2. When a mask pattern inspection was carried out with a maskinspection apparatus on the halftone phase-shift mask 200 fabricated inExample 2-2, it was confirmed that a fine pattern was formed within theacceptable range of the design value. Next, treatment was carried out onthe phase-shift pattern 2 a of this halftone phase-shift mask 200 ofExample 2-2 by irradiating with ArF excimer laser light at a cumulativedose of 20 kJ/cm². The change in CD of the phase-shift pattern 2 abefore and after this radiation treatment was about 2 nm, and thisamount of change in CD was within a usable range as a phase-shift mask.

A simulation of a transferred image was carried out on the halftonephase-shift mask 200 of Example 2-2 after undergoing radiation treatmentwith ArF excimer laser light when exposed and transferred to a resistfilm on a semiconductor device with exposure light having a wavelengthof 193 nm using the AIMS193 (Carl Zeiss AG). When this simulated exposedand transferred image was verified, it was determined to adequatelysatisfy design specifications. On the basis of this result, even if thephase-shift mask of Example 2-2 is placed on the mask stage of anexposure apparatus after being irradiated with an ArF excimer laser at acumulative dose of 20 kJ/cm² and exposed and transferred to a resistfilm on a semiconductor device, it can be said that the circuit patternultimately formed on the semiconductor device can be formed with highprecision.

Comparative Example 2-1

Next, in Comparative Example 2-1, a study was made of the case ofdepositing a halftone phase-shift film composed of a single layer ofsilicon nitride on a transparent substrate. The transparent substrate 1and single-wafer RF sputtering apparatus 30 were the same as Example2-1. The single-layer silicon nitride film was formed by RF sputteringusing the silicon (Si) target 55. A mixed gas of an inert gas in theform of argon (Ar) gas and a reactive gas in the form of nitrogen (N₂)gas was used for the sputtering gas. Sputtering conditions werepreliminarily examined for the relationship between deposition rate andthe flow rate ratio of N₂ gas in the mixed gas of Ar gas and N₂ gas usedfor the sputtering gas with the RF sputtering apparatus. As a result, itwas determined that, in order deposit a single-layer silicon nitridefilm having an extinction coefficient preferable for use as asingle-layer halftone phase-shift film, the sputtering target isrequired to be deposited in the unstable “transition mode”, therebypreventing stable deposition.

Comparative Example 2-2

Next, in Comparative Example 2-2, a study was made of the case ofalternately depositing a film in the metal mode and poison mode using asingle target. As a result, film defects were determined to increase dueto the effects of particles generated when the target mode changed. Morespecifically, when poison mode deposition (state in which the targetsurface is bound to the reactive gas) and metal mode deposition (statein which the target surface is not bound to the reactive gas) arerepeated using the same target, particles are generated when the targetmode changes. As a specific example thereof, a target material bound toreactive gas during the poison mode is stripped when the mode changes tothe metal modem, and this causes the generation of particles. Inaddition, when the same target is used, since it is necessary tore-condition the target when the reactive gas has been changed,particles may also be generated accompanying mechanical operation of ashielding plate and the like used during conditioning.

The following provides a more detailed explanation of the thirdembodiment of the present disclosure according to Example 3-1.

Example 3-1

<<Manufacturing of Mask Blank>>

The transparent substrate 301 composed of synthetic quartz glass wasprepared in which dimensions of the main surface were about 152 mm×about152 mm and thickness was about 6.35 mm. This transparent substrate 301was polished to a predetermined surface roughness for the edge faces andmain surface followed by subjecting to predetermined cleaning treatmentand drying treatment, and had concave defects F at a plurality oflocations and at a depth of not more than 40 nm.

Next, the transparent substrate 301 was placed on the rotating stage 531in the deposition chamber 535 in the deposition apparatus 500 that usesoblique incidence rotary sputtering as explained using FIGS. 8 and 9.The sputtering target 533 in the form of a silicon (Si) target wasattached to the backing plate 543. Furthermore, a deposition apparatusin which the target angle of inclination θ between the sputtered surface533 s of the sputtering target 533 and the main surface S of thetransparent substrate 301 is 15 degrees, the offset distance Doffbetween the sputtering target 533 and the transparent substrate 301 is340 mm, and the vertical distance (H) between the sputtering target 533and the transparent substrate 301 is 280 mm, was used for the depositionapparatus 500.

Next, air inside the deposition chamber 533 was evacuated through theexhaust port 539 with a vacuum pump, and after the atmosphere inside thedeposition chamber 533 had reached a degree of vacuum that does notaffect the characteristics of the thin film formed, a mixed gascontaining nitrogen was introduced from the gas inlet port 537 anddeposition was carried out by sputtering by applying RF electrical powerto the magnetron electrode 541 using an RF power supply (not shown). TheRF power supply had an arc detection function and the discharge statewas able to be monitored during sputtering. Pressure inside thedeposition chamber 535 was measured with a pressure gauge (not shown).

The high transmission layer 322 (Si:N=46 at %:54 at %), composed ofsilicon and nitrogen, was then formed at a thickness of 55 nm on themain surface S of the transparent substrate 301 by reactive sputtering(RF sputtering) by using a mixed gas of argon (Ar) and nitrogen (N₂)(flow rate ratio Ar:N₂=1:3, pressure=0.09 Pa) for the sputtering gas andsetting the electrical power of the RF power supply to 2.8 kW. When onlythe high transmission layer 322 was formed on a main surface of adifferent transparent substrate under the same conditions, and opticalcharacteristics of this high transmission layer 322 were measured usinga spectroscopic ellipsometer (M-2000D, J. A. Woollam Co., Inc.),refractive index n at a wavelength of 193 nm was 2.52 and extinctioncoefficient k was 0.39. Furthermore, conditions used when depositingthis high transmission layer 322 were such that deposition conditionssuch as flow rate ratio were selected that allowed stable deposition inthe reaction mode (poison mode) region by preliminarily verifying therelationship between deposition rate and flow rate ratio of N₂ gas inthe mixed gas of Ar gas and N₂ gas used for the sputtering gas with theRF sputtering apparatus used. Furthermore, composition of the hightransmission layer 322 was obtained by measuring by X-ray photoemissionspectroscopy (XPS). The same applies to other films as well.

Next, the low transmission layer 321 (Si:N=59 at %:41 at %) wasdeposited at a thickness of 12 nm by reactive sputtering (RF sputtering)using a mixed gas of argon (Ar) and nitrogen (N₂) gas (flow rate ratioAr:N₂=2:3, pressure=0.035 Pa) and setting the electrical power of the RFpower supply to 2.8 kW in continuation from deposition of the hightransmission layer 322. When only the low transmission layer 321 wasformed under the same conditions on a main surface of a differenttransparent substrate and optical characteristics of this lowtransmission layer 321 were measured using a spectroscopic ellipsometer(M-2000D, J. A. Woollam Co., Inc.), refractive index n at a wavelengthof 193 nm was 1.85 and extinction coefficient k was 1.70. Furthermore,conditions used when depositing this low transmission layer 321 weresuch that deposition conditions such as flow rate ratio were selectedthat allowed stable deposition in the metal mode region by preliminarilyverifying the relationship between deposition rate and flow rate ratioof N₂ gas in a mixed gas of Ar gas and N₂ gas used for the sputteringgas with the RF sputtering apparatus used.

Next, the transparent substrate 301 laminated with the high transmissionlayer 322 and the low transmission layer 321 was placed on the rotatingstage 531 in the deposition chamber 535 of the same deposition apparatus500. The sputtering target 533 in the form of a silicon oxide (SiO₂)target was attached to the backing plate 543. The uppermost layer 323,composed of silicon and oxygen, was then formed at a thickness of 4 nmon the low transmission layer 321 by RF sputtering using argon (Ar) gas(pressure=0.03 Pa) for the sputtering gas and setting the electricalpower of the RF power supply to 1.5 kW. Furthermore, when only theuppermost layer 323 was formed under the same conditions on a mainsurface of a different transparent substrate and optical characteristicsof this uppermost layer 323 were measured using a spectroscopicellipsometer (M-2000D, J. A. Woollam Co., Inc.), refractive index n at awavelength of 193 nm was 1.56 and extinction coefficient k was 0.00.

According to the aforementioned procedure, the phase-shift film 320,composed of the high transmission layer 322, the low transmission layer321 and the uppermost layer 323, was formed on the transparent substrate301. When transmittance and phase difference were measured for thisphase-shift film 320 at the wavelength of light of an ArF excimer laser(about 193 nm) with a phase shift measuring apparatus, transmittance was5.97% and phase difference was 177.7 degrees.

Next, the light shielding film 303 of a chromium-based material composedof three layers was formed at a total film thickness of 48 nm on thephase-shift film 320 according to the same procedure as that of Example1-1. Continuing, the etching mask film 304, composed of silicon andoxygen, was formed at a thickness of 5 nm on the light shielding film303 according to the same procedure as that of Example 1-1. Next, thesurface of the etching mask film 304 was subjected to HMDS treatment.Continuing, the resist film 305, composed of a chemically amplifiedresist for electron beam drawing, was formed at a film thickness of 80nm in contact with the surface of the etching mask film 304 by spincoating. According to the aforementioned procedure, the mask blank 300of Example 3-1 was manufactured provided with a structure obtained bylaminating the phase-shift film 320 having a three-layer structure, thelight shielding film 303, the etching mask film 304 and the resist film305 on the transparent substrate 301.

<<Manufacturing of Phase-Shift Mask>>

The phase-shift mask 600 of Example 3-1 was fabricated according to thesame procedure as that of Example 1-1 using the mask blank 300fabricated in the Example 3-1. However, differing from the case ofExample 1-1, a pattern design was employed in which, when drawing andexposing a phase-shift pattern to be formed on the phase-shift film 320in the form of a first pattern on the resist film 305, a concave defectF of the transparent substrate 301 was covered with the first resistpattern that does not utilize phase shift.

When a mask pattern inspection was carried out with a mask inspectionapparatus on the halftone phase-shift mask 600 fabricated in Example3-1, it was confirmed that a fine pattern was formed within theacceptable range of the design value. Next, treatment was carried out onthe phase-shift pattern of this halftone phase-shift mask 600 of Example3-1 by irradiating with ArF excimer laser light at a cumulative dose of20 kJ/cm². The change in CD of the phase-shift pattern before and afterthis radiation treatment was about 2 nm, and this amount of change in CDwas within a usable range as a phase-shift mask.

A simulation of a transferred image was carried out on the halftonephase-shift mask 600 of Example 3-1 after undergoing radiation treatmentwith ArF excimer laser light when exposed and transferred to a resistfilm on a semiconductor device with exposure light having a wavelengthof 193 nm using the AIMS193 (Carl Zeiss AG). When this simulated exposedand transferred image was verified, it was determined to adequatelysatisfy design specifications. On the basis of this result, even ifexposed and transferred to a resist film on a substrate in themanufacturing process of a semiconductor device, it can be said that thecircuit pattern ultimately formed on the semiconductor device can beformed with high precision even if the concave defect F is present onthe main surface S of the transparent substrate 301 as a result ofemploying a configuration in which it is covered with the transferpattern 320 a composed of the large-area phase-shift film 320 that doesnot utilize phase shift.

Although the preceding description has provided a detailed explanationof specific examples of the present disclosure, these examples aremerely intended to be exemplary and do not limit the scope of claim forpatent. Various variations and modifications of the previouslyexemplified specific examples are included in the art described in thescope of claim for patent. One example thereof is an etching stopperfilm formed between a transparent substrate and a phase-shift film. Anetching stopper film is a film composed of material that has etchingselectivity for both the transparent substrate and the phase-shift film.In terms of the configurations of the aforementioned examples, amaterial containing chromium, such as Cr, CrN, CrC, CrO, CrON and CrC,is suitable for the etching mask film.

Technical elements explained in the present description or drawingsdemonstrate technical usefulness either alone or by combining varioustypes thereof, and are not limited to the combinations described in theclaims at the time of filing. In addition, the technology exemplified inthe present description or drawings is able to achieve a plurality ofaspects simultaneously, and the achievement per se of one of thoseaspects has technical usefulness.

BRIEF DESCRIPTION OF THE REFERENCE SYMBOLS

-   -   1, 301 Transparent substrate    -   2, 320 Phase-shift film    -   2 a Phase-shift pattern    -   3, 303 Light shielding film    -   3 a, 3 b Light shielding pattern    -   4, 304 Etching mask film    -   4 a Etching mask pattern    -   5 a First resist pattern    -   6 b Second resist pattern    -   21, 321 Low transmission layer    -   22, 322 High transmission layer    -   23, 323 Uppermost layer (oxidized layer)    -   30 Single-wafer RF sputtering apparatus    -   32 Vacuum chamber    -   34 Main valve    -   35 Substrate holder    -   36 Vacuum pump    -   40 Inert gas supply source    -   44 Reactive gas supply source    -   48 Pressure gauge    -   50, 60 RF power supply    -   52, 62 Target holder    -   53, 63 Backing plate    -   55, 65 Target    -   56, 66 Cylindrical chamber    -   100, 101, 300 Mask blank    -   200 Transfer mask    -   303 a Pattern formation region    -   303 b Outer peripheral region    -   320 a Transfer pattern composed of large-area phase-shift film    -   350 Transfer pattern    -   500 Deposition apparatus    -   531 Rotating stage    -   533 Sputtering target    -   533 s Sputtered surface    -   535 Deposition chamber    -   537 Gas inlet port    -   539 Exhaust port    -   541 Magnetron electrode    -   543 Backing plate    -   600 Phase-shift mask    -   D Low-density region    -   F Concave defect    -   S Main surface

The invention claimed is:
 1. A mask blank comprising: a transparentsubstrate; and a phase-shift film provided on the transparent substrate,wherein a transmittance of the phase-shift film with respect to ArFexposure light is within a range of from 1% to 30%, and wherein thephase-shift film is configured to shift a phase of ArF exposure lighttransmitted through the phase-shift film by a phase shift amount that iswithin a range of from 170 degrees to 190 degrees, the phase shiftamount being relative to a phase of ArF exposure light transmittedthrough air over a same distance as a thickness of the phase-shift film,and wherein a nitrogen-containing layer of the phase-shift film isformed from a material containing silicon and nitrogen and does notcontain a transition metal, and wherein a content of oxygen in thenitrogen-containing layer, when measured by X-ray photoemissionspectroscopy, is below a detection limit, and wherein thenitrogen-containing layer has, with respect to ArF exposure light, arefractive index n that is not less than 2.5 and a extinctioncoefficient k that is less than 1.0 and not less than 0.39.
 2. The maskblank according to claim 1, wherein the nitrogen content of thenitrogen-containing layer is more than 41 at % and not more than 54 at%.
 3. The mask blank according to claim 1, wherein thenitrogen-containing layer is formed from a material consistingessentially of silicon and nitrogen or from a material consistingessentially of silicon, nitrogen, and one or more elements selected fromthe group consisting of semi-metallic elements, non-metallic elements,and noble gases.
 4. The mask blank according to claim 1, wherein thenitrogen-containing layer is formed from a material consistingessentially of silicon and nitrogen.
 5. The mask blank according toclaim 1, wherein the phase-shift film is provided with an uppermostlayer formed at a position farthest away from the transparent substrate,and wherein the uppermost layer is formed from a material consistingessentially of silicon, nitrogen, and oxygen or from a materialconsisting essentially of silicon, nitrogen, oxygen, and one or moreelements selected from the group consisting of semi-metallic elements,non-metallic elements, and noble gases.
 6. The mask blank according toclaim 5, wherein the uppermost layer is formed from a materialconsisting essentially of silicon, nitrogen, and oxygen.
 7. The maskblank according to claim 5, wherein the oxygen content of the uppermostlayer increases with distance from the transparent substrate.
 8. Themask blank according to claim 5, wherein the uppermost layer is formedfrom a material consisting essentially of silicon and oxygen.
 9. Themask blank according to claim 1, wherein the nitrogen-containing layeris in contact with a surface of the transparent substrate.
 10. Aphase-shift mask comprising: a transparent substrate; and a phase-shiftfilm provided on the transparent substrate, the phase-shift film havinga transfer pattern, wherein a transmittance of the phase-shift film withrespect to ArF exposure light is within a range of from 1% to 30%, andwherein the phase-shift film is configured to shift a phase of ArFexposure light transmitted through the phase-shift film by a phase shiftamount that is within a range of from 170 degrees to 190 degrees, thephase shift amount being relative to a phase of ArF exposure lighttransmitted through air over a same distance as a thickness of thephase-shift film, and wherein a nitrogen-containing layer of thephase-shift film is formed from a material containing silicon andnitrogen and does not contain a transition metal, and wherein a contentof oxygen in the nitrogen-containing layer, when measured by X-rayphotoemission spectroscopy, is below a detection limit, and wherein thenitrogen-containing layer has, with respect to ArF exposure light, arefractive index n that is not less than 2.5 and a extinctioncoefficient k that is less than 1.0 and not less than 0.39.
 11. Thephase-shift mask according to claim 10, wherein the nitrogen content ofthe nitrogen-containing layer is more than 41 at % and not more than 54at %.
 12. The phase-shift mask according to claim 10, wherein thenitrogen-containing layer is formed from a material consistingessentially of silicon and nitrogen or from a material consistingessentially of silicon, nitrogen, and one or more elements selected fromthe group consisting of semi-metallic elements, non-metallic elements,and noble gases.
 13. The phase-shift mask according to claim 10, whereinthe nitrogen-containing layer is formed from a material consistingessentially of silicon and nitrogen.
 14. The phase-shift mask accordingto claim 10, wherein the phase-shift film is provided with an uppermostlayer formed at a position farthest away from the transparent substrate,and wherein the uppermost layer is formed from a material consistingessentially of silicon, nitrogen, and oxygen or from a materialconsisting essentially of silicon, nitrogen, oxygen, and one or moreelements selected from the group consisting of semi-metallic elements,non-metallic elements, and noble gases.
 15. The phase-shift maskaccording to claim 14, wherein the uppermost layer is formed from amaterial consisting essentially of silicon, nitrogen, and oxygen. 16.The phase-shift mask according to claim 14, wherein the oxygen contentof the uppermost layer increases with distance from the transparentsubstrate.
 17. The phase-shift mask according to claim 14, wherein theuppermost layer is formed from a material consisting essentially ofsilicon and oxygen.
 18. The phase-shift mask according to claim 10,wherein the nitrogen-containing layer is in contact with a surface ofthe transparent substrate.
 19. A method for manufacturing asemiconductor device, the method comprising using a phase-shift mask toexpose and transfer a transfer pattern to a resist film on asemiconductor substrate, the phase-shift mask comprising: a transparentsubstrate; and a phase-shift film provided on the transparent substrate,the phase-shift film having a transfer pattern, wherein a transmittanceof the phase-shift film with respect to ArF exposure light is within arange of from 1% to 30%, and wherein the phase-shift film is configuredto shift a phase of ArF exposure light transmitted through thephase-shift film by a phase shift amount that is within a range of from170 degrees to 190 degrees, the phase shift amount being relative to aphase of ArF exposure light transmitted through air over a same distanceas a thickness of the phase-shift film, and wherein anitrogen-containing layer of the phase-shift film is formed from amaterial containing silicon and nitrogen and does not contain atransition metal, and wherein a content of oxygen in thenitrogen-containing layer, when measured by X-ray photoemissionspectroscopy, is below a detection limit, and wherein thenitrogen-containing layer has, with respect to ArF exposure light, arefractive index n that is not less than 2.5 and a extinctioncoefficient k that is less than 1.0 and not less than 0.39.
 20. Themethod for manufacturing a semiconductor device according to claim 19,wherein the nitrogen-containing layer is formed from a materialconsisting essentially of silicon and nitrogen or from a materialconsisting essentially of silicon, nitrogen, and one or more elementsselected from the group consisting of semi-metallic elements,non-metallic elements, and noble gases.